PHOSPHORUS-CONTAINING CATALYSTS

摘要

The invention provides compounds of general structure I: (Ar1—Ar2—Ar3-E-P(=D)R2-)nMmXnLn″. In this structure: •Ar1, Ar2 and Ar3 are aromatic groups wherein: —Ar1 and Ar3 are in a 1,3 relationship on Ar2, —each of Ar1, Ar2 and Ar3 optionally comprises one or more ring substituents of formula YR′r wherein each Y independently is absent or is O, S, B, N or Si and each R′ is independently H, halogen, alkyl, cycloalkyl, aryl or heteroaryl and r is 1, 2 or 3, where r is 1 if Y is absent or is O or S, 2 if Y is B or N and 3 if Y is Si, —Ar1, Ar2 and Ar3 are each independently carbocyclic or heterocyclic and each is independently monocyclic, bicyclic or polycyclic and each ring of each of Ar1, Ar2 and Ar3 independently has 5, 6 or 7 ring atoms; •E is absent or is selected from the group consisting of O, S, NR″, SiR″2, AsR″2 and CR″2; •M is a complexing metal; •X is selected from the group consisting of H, F, Br, CI, I, OTf, dba (dibenzylidene acetone), OC(═O)CF3 and OAc; •L is selected from the group consisting of PR″2, NR″2, OR″, SR″, SiR″3, AsR″3, alkene, alkyne, aryl and heteroaryl, each of said alkene, alkyne, aryl and heteroaryl being optionally substituted, for example with one or more halogens and/or with one or more R groups as defined herein; •each R is independently alkyl, cycloalkyl, heterocyclyl, heterocycloalkyl, aryl or -, heteroaryl; •D is absent or is ═S or —O or —Z-linker-Z—, where each Z independently is O or NH or N-alkyl and linker is an alkyl chain of 2-5 carbon atoms in length; •each R″ is independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, each other than H being optionally substituted, or R″2 is —Z-linker-Z— as defined above; and •m is 0 or 1 or 2; wherein if m is 0, n is 1, n′ and n″ are 0 and -- is absent; and if m is 1 or 2, n is 1 or 2 and n′ and n″ are integers such that the coordination sphere of M is filled, and D is absent.

主权项

1. A compound of structure I:
(Ar1—Ar2—Ar3-E-P(=D)R2—-)nMmXn′Ln″wherein:
Ar1, Ar2 and Ar3 are aromatic groups wherein: Ar1 and Ar3 are in a 1,3 relationship on Ar2, each of Ar1, Ar2 and Ar3 optionally comprises one or more ring substituents of formula YR′r wherein each Y independently is absent or is O, S, B, N or Si and each R′ is independently H, halogen, alkyl, cycloalkyl, aryl or heteroaryl and r is 1, 2 or 3, where r is 1 if Y is absent or is O or S, 2 if Y is B or N and 3 if Y is Si, Ar1, Ar2 and Ar3 are each independently carbocyclic or heterocyclic and each is independently monocyclic, bicyclic or polycyclic and each ring of each of Ar1, Ar2 and Ar3 independently has 5, 6 or 7 ring atoms; E is absent or is selected from the group consisting of O, S, NR″, SiR″2, AsR″2 and CR″2; M is a complexing metal; X is selected from the group consisting of H, F, Br, Cl, I, OTf, dba (dibenzylidene acetone), OC(═O)CF3 and OAc; L is absent or is selected from the group consisting of PR″2, NR″2, OR″, SR″, SiR″3, AsR″3, alkene, alkyne, aryl and heteroaryl, each of said alkene, alkyne, aryl and heteroaryl being optionally substituted, for example with one or more halogens and/or with one or more R groups as defined herein, wherein if L is absent, n is not 1; each R is independently alkyl, cycloalkyl, heterocyclyl, heterocycloalkyl, aryl, heteroaryl, alkyloxy, cycloalkyloxy, heterocyclyloxy, heterocycloalkyloxy, aryloxy or heteroaryloxy; D is absent or is ═S or ═O or —Z-linker-Z—, where each Z independently is O or NH or N-alkyl and linker is an alkyl chain of 2-5 carbon atoms in length; each R″ is independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, each other than H being optionally substituted, or R″2 is —Z-linker-Z— as defined above; and m is 0 or 1 or 2; wherein: if m is 0, n is 1, n′ and n″ are 0 and -- is absent; and if m is 1 or 2, n is 1 or 2 and n′ and n″ are integers such that the coordination sphere of M is filled, and D is absent.