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US 2006/0069277 A1Published application
Chiral organometallic compounds for use in asymmetric synthesis
AssigneeAvecia Limited
InventorRichard Whitby
Life of this patent
Estimating the term…
Abstract
Chiral organometallic compounds are provided which comprise certain non-symmetrically substituted cyclopentadiene complexed to a transition metal. The cyclopentadiene has a second coordinating group which also complexes the transition metal and is attached to the cyclopentadiene by means of a chiral connecting chain. Preferred transition metals include rhodium, ruthenium, iridium, cobalt, iron, manganese, chromium, tungsten, molybdenum, nickel, palladium, or platinum. These chiral organometallic compounds find use in asymmetric synthesis to produce chiral compounds.
Claims16
A compound of formula (1):
- wherein:
- L is optionally one or more groups which are removable during a chemical reaction;
- M is a transition metal selected from Groups 6, 7, 8, 9 and 10;
- Y is an optionally substituted linking group;
- A is an optionally substituted heteroatom capable of bonding or coordinating to metal (M);
- and
- EITHER:
- (a) R5 and R6 are hydrogen:
- R1 is optionally substituted hydrocarbyl, optionally substituted heterocyclyl, or tri-hydrocarbylsilyl, or R1 & Y are linked in such a way as to form an asymmetrically substituted ring, or R1 & A are linked in such a way as to form an optionally substituted heterocyclic ring;
- R2 is optionally substituted hydrocarbyl, optionally substituted heterocyclyl, or tri-hydrocarbylsilyl;
- R3 and R4 are independently optionally substituted hydrocarbyl, optionally substituted heterocyclyl, tri-hydrocarbylsilyl or hydrogen;
- or
- one or more of R2 & R3 and R3 & R4 are linked in such a way as to form an optionally substituted ring optionally comprising one or more heteroatoms;
- provided that R2, R3 and R4 are selected such that the cyclopentadiene ring to which they are attached is asymmetrically substituted;
- OR:
- (b) R3 is hydrogen, optionally substituted hydrocarbyl, optionally substituted heterocyclyl, or tri-hydrocarbylsilyl;
- and either
- (i) R5 & R2 are linked in such a way as to form an optionally substituted non-aromatic ring system optionally comprising one or more heteroatoms;
- and
- R4, R4 and R6 are independently hydrogen, optionally substituted hydrocarbyl, optionally substituted heterocyclyl, or tri-hydrocarbylsilyl;
- or
- R1 & R6 are linked in such a way as to form an optionally substituted non-aromatic ring system optionally comprising one or more heteroatoms and R4 is hydrogen, optionally substituted hydrocarbyl, optionally substituted heterocyclyl, or tri-hydrocarbylsilyl;
- or
- R4 & R6 are linked in such a way as to form an optionally substituted ring optionally comprising one or more heteroatoms and R1 is hydrogen, optionally substituted hydrocarbyl, optionally substituted heterocyclyl, or tri-hydrocarbylsilyl;
- or
- (ii) R5, R1 & R2 are linked in such a way as to form an optionally substituted non-aromatic asymmetric ring system optionally comprising one or more heteroatoms;
- and R4 and R6 are idependently hydrogen, optionally substituted hydrocarbyl, optionally substituted heterocyclyl, or tri-hydrocarbylsilyl;
- or R4 & R6 are linked in such a way as to form an optionally substituted ring optionally comprising one or more heteroatoms.
25 more elements
A compound of formula (1);
- wherein:
- L is, independently, one or more groups which are removable during a chemical reaction;
- M is rhodium, ruthenium, iridium, cobalt, iron, manganese, chromium, tungsten, molybdenum, nickel, palladium, or platinum;
- Y is a linking chain comprising an optionally substituted C1-5 alkyl or alkylaryl, or optionally substituted silyl bridge, or optionally substituted heteroatom containing bridge;
- A is an atom (which may carry substituents) which may bond to the metal;
- EITHER:
- (a) R5 and R6 are hydrogen;
- R1 and R2 are trialkylsilyl, dialkylarylsilyl, alkyldiarylsilyl, triarylsilyl, alkyl, aryl, arylalkyl, aryloxyalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or heteroaryloxyalkyl;
- or R2 is as above and R1 joins to Y to form an asymmetrically substituted C3-8 cycloalkyl, C3-8 cycloalkenyl or C3-8 heterocyclyl ring optionally substituted with hydroxy, trialkylsilyl, alkyl, alkoxy, aryl, arylalkyl, aryloxyallyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalky, cycloalkylalkyl, heteroaryl, heteroarylalkyl or heteroaryloxyalkyl;
- or R2 is as above and R1 joins to A to form an optionally substituted heterocyclic ring;
- R3 and R4 are the same or different and are selected from the substituents already recited for R1 and R2 and may also be, independently, hydrogen;
- or, one or more of R2 and R3, R3 and R4 join to form an optionally substituted ring optionally comprising one or more heteroatoms OR:
- (b) R3 is hydrogen, trialkylsilyl, dialkylarylsilyl, alkyldiarylsilyl, triarylsilyl, alkyl, aryl, arylalkyl, aryloxyalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or heteroaryloxyalkyl;
- and either
- (i) R5 and R2 join to form an optionally substituted non-aromatic ring system optionally comprising one or more heteroatoms;
- and
- R1, R4 and R5 are independently hydrogen, trialkylsilyl, dialkylarylsilyl, alkyldiarylsilyl, triarylsilyl, alkyl, aryl, arylalkyl, aryloxyalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or heteroaryloxyalkyl;
- or
- R1 & R6 join to form an optionally substituted non-aromatic ring system optionally comprising one or more heteroatoms and R4 is hydrogen, trialkylsilyl, dialkylarylsilyl, alkyldiarylsilyl, triarylsilyl, alkyl, aryl, arylalkyl, aryloxyalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or heteroaryloxyalkyl;
- or
- R4 & R6 join to form an optionally substituted ring system optionally comprising one or more heteroatoms and R1 is hydrogen, trialkylsilyl, dialkylarylsilyl, alkyldiarylsilyl, triarylsilyl, alkyl, aryl, arylalkyl, aryloxyalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or heteroaryloxyalkyl;
- or
- (ii) R5, R1 and R2 are linked in such a way as to form an optionally substituted non-aromatic asymmetric ring system comprising one or more heteroatoms;
- and R4 and R6 is hydrogen, trialkylsilyl, dialkylarylsilyl, alkyldiarylsilyl, triarylsilyl, alkyl, aryl, arylalkyl, aryloxyalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or heteroaryloxyalkyl;
- or R4 & R6 join to form an optionally substituted ring system optionally comprising one or more heteroatoms.
22 more elements
A compound of Formula (2) or (3):
- wherein:
- L are independently one or more groups which are removable during a chemical reaction;
- M is rhodium, ruthenium, iridium, cobalt, iron, manganese, chromium, tungsten, molybdenum, nickel, palladium, or platinum;
- Y is a linking chain comprising an optionally substituted C1-5alkyl or alkylaryl, or optionally substituted silyl bridge, or optionally substituted hetereoatom containing bridge;
- A is an atom (which may carry substituents) which may bond to the metal;
- R1 is trialkylsilyl, dialkylarylsilyl, alkyldiarylsilyl, triarylsilyl, alkyl, aryl, arylalkyl, aryloxyalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or heteroaryloxyalkyl;
- or R1 joins to Y to form an asymmetrically substituted C3-8cycloalkyl, C3-8cycloalkenyl or C3-8heterocyclyl ring optionally substituted with hydroxy, trialkylsilyl, alkyl, alkoxy, aryl, arylalkyl, aryloxyallyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalky, cycloalkylalkyl, heteroaryl, heteroarylalkyl or heteroaryloxyalkyl;
- or R1 joins to A to form an optionally substituted heterocyclic ring;
- R4 is hydrogen, trialkylsilyl, dialkylarylsilyl, alkyldiarylsilyl, triarylsilyl, alkyl, aryl, arylalkyl, aryloxyalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or heteroaryloxyalkyl;
- R6 is hydrogen;
- and
- T1, T2, T3, T4 are the same or different and are hydrogen, trialkylsilyl, dialkylarylsilyl, alkyldiarylsilyl, triarylsilyl, alkyl, aryl, arylalkyl, aryloxyalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or heteroaryloxyalkyl.
9 more elements
A compound of formula (4) or (5):
- wherein:
- L is independently one or more groups which are removable during a chemical reaction;
- M is rhodium, ruthenium, iridium, cobalt, iron, manganese, chromium, tungsten, molybdenum, nickel, palladium, or platinum;
- Y is a linking chain comprising an optionally substituted C1-5alkyl or alkylaryl, or optionally substituted silyl bridge, or optionally substituted hetereoatom containing bridge;
- A is an atom (which may carry substituents) which may bond to the metal;
- B is a bridge comprising an optionally substituted C1-3alkyl bridge or an optionally substituted 1-3 atom bridge wherein at least one atom is a heteroatom and any remaining atoms are carbon atoms, preferably wherein any heteroatoms are selected from the group comprising N, O, P, S and Si;
- Y is an optionally substituted C1-3alkyl bridge;
- and
- R3, R4, R6, R8, R9, Q1, Q2, Q3, Q4, Q5, Q6, Q7 are the same or different and are hydrogen, trialkylsilyl, dialkylarylsilyl, alkyldiarylsilyl, triarylsilyl, alkyl, aryl, arylalkyl, aryloxyalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or heteroaryloxyalkyl;
- or
- R4 & R6 are linked in such a way as to form an optionally substituted ring optionally comprising one or more heteroatoms;
- or
- Q4 & R6 are linked in such a way as to form an optionally substituted non-aromatic ring system comprising one or more heteratoms;
- and additionally
- Q2 and Q3 may also be alkoxy, aryloxy or silyloxy;
- or Q2 and Q3 combine to form a carbonyl, mine, or alkylidene group.
13 more elements
(canceled)
Dependencies are inferred from the claim text.