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US 5,296,595 AGranted
Method of enantioselectively inserting a carbene
AssigneeResearch Corporation Technologies, Inc.
InventorMichael P. Doyle
Life of this patent
Estimating the term…
Abstract
A chiral catalyst is disclosed together with methods of using it for enantioselective syntheses. The chiral catalyst includes a nucleus with two metal atoms that has four bridging ligands oriented radially to the axis of the nucleus. Each of these ligands includes a two complexing atoms each complexed to one of the metal atoms. At least one of the bridging ligands includes a chiral center which is bonded to one of the complexing atoms. Preferably, all four of the bridging ligands include a chiral center bonded to one of the complexing atoms. The catalyst of the invention has been found to be useful in catalyzing carbenoid transformation reactions such as cyclopropanation.
Claims53
A method of enantioselectively inserting a carbene between a carbon and a hydrogen comprising the steps of:
- providing a compound with a carbon-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed to said second metal atom,
- said first bridging ligand further comprising a ring including said first complexing atom and attached to said second complexing atom, said ring also including a chiral center attached through a first bonding site to said first complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent, and
- said second bridging ligand further comprising a ring including said second complexing atom and attached to said first complexing atom, said ring also including a chiral center attached through a first bonding site to said second complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent, and wherein the R/S configuration of the chiral center on the second bridging ligand is the same as the R/S configuration of the chiral center on the first bridging ligand;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
8 more elements
A method of enantioselectively inserting a carbene between a carbon and a hydrogen comprising the steps of:
- providing a compound with a carbon-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed to said second metal atom,
- said first bridging ligand also comprising a ring including said first complexing atom and attached to said second complexing atom, said ring also including a chiral center attached through a first bonding site to said first complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent, and
- said first bridging ligand further comprising a second chiral center attached through a first bonding site to said second complexing atom, having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
8 more elements
A method of enantioselectively inserting a carbene between a carbon and a hydrogen comprising the steps of:
- providing a compound with a carbon-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis.
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed to said second metal atom,
- said first bridging ligand also comprising a ring including said first complexing atom and attached to said second complexing atom, said ring also including a chiral center attached through a first bonding site to said first complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent;
- and
- blocking structure bonded to at least one of said first, second, third, and fourth bridging ligands, said blocking structure being constituted, configured, and oriented so as to substantially impair approach to the second metal atom along said axis;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
9 more elements
A method of enantioselectively inserting a carbene between a carbon and a hydrogen comprising the steps of:
- providing a compound with a carbon-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed with said second metal atom,
- said first bridging ligand further comprising a chiral center attached through a first bonding site to the first complexing atom, and having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent, and
- said second bridging ligand further comprising a chiral center attached through a first bonding site to the second complexing atom, and having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent, and
- wherein the R/S configuration of the chiral centers on the first and second bridging ligands are all the same;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
9 more elements
A method of enantioselectively inserting a carbene between a carbon and a hydrogen comprising the steps of:
- providing a compound with a carbon-hydrogen bond;
- providing a carbene precursor, wherein either said compound of said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed with said second metal atom,
- said first bridging ligand further comprising a chiral center attached through a first bonding site to the first complexing atom, and having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent, and
- blocking structure bonded to at least one of said first, second, third, and fourth bridging ligands, said blocking structure being constituted, configured and oriented so as to substantially impair approach to the second metal atom along said axis;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
8 more elements
A method of enantioselectively inserting a carbene between an oxygen and a hydrogen comprising the steps of:
- providing a compound with an oxygen-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed to said second metal atom,
- said first bridging ligand further comprising a ring including said first complexing atom and attached to said second complexing atom, said ring also including a chiral center attached through a first bonding site to said first complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent, and
- said second bridging ligand further comprising a ring including said second complexing atom and attached to said first complexing atom, said ring also including a chiral center attached through a first bonding site to said second complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent, and wherein the R/S configuration of the chiral center on the second bridging ligand is the same as the R/S configuration of the chiral center on the first bridging ligand;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene, insertion to proceed.
8 more elements
A method of enantioselectively inserting a carbene between an oxygen and a hydrogen comprising the steps of:
- providing a compound with an oxygen-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed to said second metal atom,
- said first bridging ligand also comprising a ring including said first complexing atom and attached to said second complexing atom, said ring also including a chiral center attached through a first bonding site to said first complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent, and
- said first bridging ligand further comprising a second chiral center attached through a first bonding site to said second complexing atom, having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
8 more elements
A method of enantioselectively inserting a carbene between an oxygen and a hydrogen comprising the steps of:
- providing a compound with an oxygen-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed to said second metal atom,
- said first bridging ligand also comprising a ring including said first complexing atom and attached to said second complexing atom, said ring also including a chiral center attached through a first bonding site to said first complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent;
- and
- blocking structure bonded to at least one of said first, second, third, and fourth bridging ligands, said blocking structure being constituted, configured, and oriented so as to substantially impair approach to the second metal atom along said axis;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
9 more elements
A method of enantioselectively inserting a carbene between an oxygen and a hydrogen comprising the steps of:
- a providing a compound with an oxygen-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed with said second metal atom,
- said first bridging ligand further comprising a chiral center attached through a first bonding site to the first complexing atom, and having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent, and
- said second bridging ligand further comprising a chiral center attached through a first bonding site to the second complexing atom, and having a second bonding site occupied by a first substituent, and having a fourth bonding site occupied by second substituent, and having a fourth bonding site occupied by a third substituent, and
- wherein the R/S configuration of the chiral centers on the first and second bridging ligands are all the same;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
9 more elements
A method of enantioselectively inserting a carbene between an oxygen and a hydrogen comprising the steps of:
- providing a compound with an oxygen-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed with said second metal atom,
- said first bridging ligand further comprising a chiral center attached through a first bonding site to the first complexing atom, and having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent, and
- blocking structure bonded to at least one of said first, second, third, and fourth bridging ligands, said blocking structure being constituted, configured and oriented so as to substantially impair approach to the second metal atom along said axis;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
8 more elements
A method of enantioselectively inserting a carbene between a nitrogen and a hydrogen comprising the steps of:
- providing a compound with a nitrogen-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed to said second metal atom,
- said first bridging ligand further comprising a ring including said first complexing atom and attached to said second complexing atom, said ring also including a chiral center attached through a first bonding site to said first complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent, and
- said second bridging ligand further comprising a ring including said second complexing atom and attached to said first complexing atom, said ring also including a chiral center attached through a first bonding site to said second complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent, and wherein the R/S configuration of the chiral center on the second bridging ligand is the same as the R/S configuration of the chiral center on the first bridging ligand;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
8 more elements
A method of enantioselectively inserting a carbene between a nitrogen and a hydrogen comprising the steps of:
- providing a compound with a nitrogen-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed to said second metal atom,
- said first bridging ligand also comprising a ring including said first complexing atom and attached to said second complexing atom, said ring also including a chiral center attached through a first bonding site to said first complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent, and
- said first bridging ligand further comprising a second chiral center attached through a first bonding site to said second complexing atom, having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
8 more elements
A method of enantioselectively inserting a carbene between a nitrogen and a hydrogen comprising the steps of:
- providing a compound with a nitrogen-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed to said second metal atom,
- said first bridging ligand also comprising a ring including said first complexing atom and attached to said second complexing atom, said ring also including a chiral center attached through a first bonding site to said first complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent;
- and
- blocking structure bonded to at least one of said first, second, third, and fourth bridging ligands, said blocking structure being constituted, configured, and oriented so as to substantially impair approach to the second metal atom along said axis;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
9 more elements
A method of enantioselectively inserting a carbene between a nitrogen and a hydrogen comprising the steps of:
- providing a compound with a nitrogen-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed with said second metal atom,
- said first bridging ligand further comprising a chiral center attached through a first bonding site to the first complexing atom, and having a third bonding site occupied by a a first substituent having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent, and
- said second bridging ligand further comprising a chiral center attached through a first bonding site to the second complexing atom, and having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent, and
- wherein the R/S configuration of the chiral centers on the first and second bridging ligands are all the same;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
9 more elements
A method of enantioselectively inserting a carbene between a nitrogen and a hydrogen comprising the steps of:
- providing a compound with a nitrogen-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed with said second metal atom,
- said first bridging ligand further comprising a chiral center attached through a first bonding site to the first complexing atom, and having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent, and
- blocking structure bonded to at least one of said first, second, third, and fourth bridging ligands, said blocking structure being constituted, configured and oriented so as to substantially impair approach to the second metal atom along said axis;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
8 more elements
A method of enantioselectively inserting a carbene between a silicon and a hydrogen comprising the steps of:
- providing a compound with a silicon-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed to said second metal atom,
- said first bridging ligand further comprising a ring including said first completing atom and attached to said second complexing atom, said ring also including a chiral center attached through a first bonding site to said first complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent, and
- said second bridging ligand further comprising a ring including said second complexing atom and attached to said first complexing atom, said ring also including a chiral center attached through a first bonding site to said second complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent, and wherein the R/S configuration of the chiral center on the second bridging ligand is the same as the R/S configuration of the chiral center on the first bridging ligand;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
8 more elements
A method of enantioselectively inserting a carbene between a silicon and a hydrogen comprising the steps of:
- providing a compound with a silicon-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed to said second metal atom,
- said first bridging ligand also comprising a ring including said first complexing atom and attached to said second complexing atom, said ring also including a chiral center attached through a first bonding site to said first complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent, and
- said first bridging ligand further comprising a second chiral center attached through a first bonding site to said second complexing atom, having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to said carbene insertion to proceed.
8 more elements
A method of enantioselectively inserting a carbene between a silicon and a hydrogen comprising the steps of:
- providing a compound with a silicon-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexing to said second metal atom,
- said first bridging ligand also comprising a ring including said first complexing atom and attached to said second complexing atom, said ring also including a chiral center attached through a first bonding site to said first complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a forth bonding site occupied by a second substituent;
- and
- blocking structure bonded to at least one of said first, second, third, and fourth bridging ligands, said blocking structure being constituted, configured, and oriented so as to substantially impair approach to the second metal atom along said axis;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
9 more elements
A method of enantioselectively inserting a carbene between a silicon and a hydrogen comprising the steps of:
- providing a compound with a silicon-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexing with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed with said second metal atom,
- said first bridging ligand further comprising a chiral center attached through a first bonding site to the first complexing atom, and having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent, and
- said second bridging ligand further comprising a chiral center attached through a first bonding site to the second complexing atom, and having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent, and
- wherein the R/S configuration of the chiral centers on the first and second bridging ligands are all the same;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
9 more elements
A method of enantioselectively inserting a carbene between a silicon and a hydrogen comprising the steps of:
- providing a compound with a silicon-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first completing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed with said second metal atom,
- said first bridging ligand further comprising a chiral center attached through a first bonding site to the first complexing atom, and having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent, and
- blocking structure bonded to at least one of said first, second, third, and fourth bridging ligands, said blocking structure being constituted, configured and oriented so as to substantially impair approach to the second metal atom along said axis;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
8 more elements
A method of enantioselectively inserting a carbene between a sulfur and a hydrogen comprising the steps of:
- providing a compound with a sulfur-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed to said second metal atom,
- said first bridging ligand further comprising a ring including said first complexing atom and attached to said second complexing atom, said rig also including a chiral center attached through a first bonding site to said first complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent, and
- said second bridging ligand further comprising a ring including said second complexing atom and attached to said first complexing atom, said ring also including a chiral center attached through a first bonding site to said second complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent, and wherein the R/S configuration of the chiral center on the second bridging ligand is the same as the R/S configuration of the chiral center on the first bridging ligand;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
8 more elements
A method of enantioselectively inserting a carbene between a sulfur and a hydrogen comprising the steps of:
- providing a compound with a sulfur-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed to said second metal atom,
- said first bridging ligand also comprising a ring including said first complexing atom and attached to said second complexing atom, said ring also including a chiral center attached through a first bonding site to said first complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent, and
- sad first bridging ligand further comprising a second chiral center attached through a first bonding site to said second complexing atom, having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
8 more elements
A method of enantioselectively inserting a carbene between a sulfur and a hydrogen comprising the steps of:
- providing a compound with a sulfur-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed to said second metal atom,
- said first bridging ligand also comprising a ring including said first complexing atom and attached to said second complexing atom, said ring also including a chiral center attached through a first bonding site to said first complexing atom, attached through a second bonding site to said ring, having a third bonding site occupied by a first substituent, and having a fourth bonding site occupied by a second substituent;
- and
- blocking structure bonded to at least one of said first, second, third, and fourth bridging ligands, said blocking structure being constituted, configured, and oriented so as to substantially impair approach to the second metal atom along said axis;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
9 more elements
A method of enantioselectively inserting a carbene between a sulfur and a hydrogen comprising the steps of:
- providing a compound with a sulfur-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed with said second metal atom,
- said first bridging ligand further comprising a chiral center attached through a first bonding site to the first complexing atom, sand having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent, and
- said second bridging ligand further comprising a chiral center attached through a first bonding site to the second complexing atom, and having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent, and
- wherein the R/S configuration of the chiral centers on the first and second bridging ligands are all the same;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
9 more elements
A method of enantioselectively inserting a carbene between a sulfur and a hydrogen comprising the steps of:
- providing a compound with a sulfur-hydrogen bond;
- providing a carbene precursor, wherein either said compound or said carbene precursor is prochiral;
- providing a chiral catalyst comprising
- a nucleus with a first and second atom of the same metal aligned on an axis, said metal selected from the group consisting of rhodium, ruthenium, chromium, molybdenum, tungsten, rhenium and osmium;
- and
- first, second, third and fourth bridging ligands oriented radially to the axis,
- each ligand having a first and second complexing atom, the first complexing atom of each of said bridging ligands being complexed with said first metal atom, and the second complexing atom of each of said bridging ligands being complexed with said second metal atom,
- said first bridging ligand further comprising a chiral center attached through a first bonding site to the first complexing atom, and having a second bonding site occupied by a first substituent, having a third bonding site occupied by a second substituent, and having a fourth bonding site occupied by a third substituent, and
- blocking structure bonded to at least one of said first, second, third, and fourth bridging ligands, said blocking structure being constituted, configured and oriented so as to substantially impair approach to the second metal atom along said axis;
- and
- reacting said compound, said carbene precursor, and said chiral catalyst under conditions sufficient to cause said carbene insertion to proceed.
8 more elements
Dependencies are inferred from the claim text.