Cyclopentadienyl derivatives and their uses in catalysis
AssigneeSigma-Aldrich Co.
InventorsTharique Nalakath, Guolin Xu, Thomas Colacot
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Abstract
Provided are ferrocenyl-based phosphine compounds, which contain either (i) a di(adamantyl)phosphino group on a first cyclopentadienide ring and a penta-aryl substitution on a second cyclopentadienide ring, or (ii) a di(adamantyl)phosphino group on a first cyclopentadienide ring and a second cyclopentadienide ring, respectively. Further provided are scalable processes for synthesizing said ferrocenyl-based phosphine compounds starting from readily available starting materials with simple workup as well as various precatalysts containing a transition metal and said ferrocenyl-based phosphine compounds as ligands.
Claims29
A compound of Formula I:
- wherein:
- Cp1 is represented by Formula II or Formula III
- R1 is at each occurrence independently from each other selected from optionally substituted C6-C10 aryl or C3-C9 heteroaryl;
- Ad is adamantyl;
- and
- each optional substituent, when present, is selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkoxy.
A precatalyst of Formula VI or Formula VII:
- wherein:
- R1 is at each occurrence independently from each other selected from optionally substituted C6-C10 aryl or C3-C9 heteroaryl;
- Ad is adamantyl;
- M is a transition metal selected from Group 9, Group 10 or Group 11;
- X is selected from the group consisting of halide, triflate (TfO−), tetrafluoroborate (BF4−), hexafluorophosphate (PF6−), mesylate (MsO−), tosylate (TsO−), tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (B[(CF3)2C6H3]4−), hexafluoroantimonate (SbF6−) and combinations thereof;
- Ar is optionally substituted C6-C10 aryl;
- and
- each optional substituent, when present, is selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkoxy.
A precatalyst of Formula VIII or Formula IX:
- wherein:
- R1 is at each occurrence independently from each other selected from optionally substituted C6-C10 aryl or C3-C9 heteroaryl;
- Ad is adamantyl;
- M is a transition metal selected from Group 9, Group 10 or Group 11;
- X is selected from the group consisting of halide, triflate (TfO−), tetrafluoroborate (BF4−), hexafluorophosphate (PF6−), mesylate (MsO−), tosylate (TsO−), tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (B[(CF3)2C6H3]4−), hexafluoroantimonate (SbF6−) and combinations thereof;
- R2 is selected from the group consisting of H, C1-C4 alkyl and C6-C10 aryl;
- and
- each optional substituent, when present, is selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkoxy.
A precatalyst of Formula X or Formula XI:
- wherein:
- R1 is at each occurrence independently from each other selected from optionally substituted C6-C10 aryl or C3-C9 heteroaryl;
- Ad is adamantyl;
- M is a transition metal selected from Group 9, Group 10 or Group 11;
- X is selected from the group consisting of halide, triflate (TfO−), tetrafluoroborate (BF4−), hexafluorophosphate (PF6−), mesylate (MsO−), tosylate (TsO−), tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (B[(CF3)2C6H3]4−), hexafluoroantimonate (SbF6−) and combinations thereof;
- R3 is selected from the group consisting of H, Me, NHMe, Ph, and NHPh;
- and
- each optional substituent, when present, is selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkoxy.
Dependencies are inferred from the claim text.