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US 2019/0314799 A1Published application
Halogen-containing metathesis catalysts and methods thereof
AssigneesMassachusetts Institute of Technology, The Trustees of Boston College
InventorsAmir H. Hoveyda, Ming Joo Koh, Thach T. Nguyen, Richard R. Schrock, Jakub Hyvl
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Abstract
The present disclosure provides compounds, compositions, and methods for preparing alkenyl halides and/or haloalkyl-substituted olefins with Z-selectivity. The methods are particularly useful for preparing alkenyl fluorides such as CF3-substituted olefins by means of cross-metathesis reactions using halogen-containing molybdenum and tungsten complexes.
Claims22
A compound of formula I-a or I-b:
- wherein
- M is molybdenum in the compound of formula I-a, or M is tungsten in the compound of formula I-b;
- R1 is a group selected from
- C1-20 aliphatic, or C1-20 heteroaliphatic having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur;
- or
- a 3-7 membered saturated carbocyclic ring, or an 8-10 membered bicyclic or tricyclic saturated ring;
- or
- a 4-7 membered saturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or a 7-10 membered bicyclic saturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, and sulfur;
- or
- an aryl ring, a 5-6 membered heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, and sulfur;
- each of R2 and R3 is independently hydrogen or a group selected from C1-20 aliphatic, C1-20 heteroaliphatic having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or aryl;
- R4 is a group selected from
- C1-20 aliphatic, or C1-20 heteroaliphatic having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur;
- or
- a 3-7 membered saturated carbocyclic ring, or an 8-10 membered bicyclic or tricyclic saturated ring;
- or
- a 4-7 membered saturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or a 7-10 membered bicyclic saturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, and sulfur;
- or
- an aryl ring, a 5-6 membered heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or an 8-14 membered bicyclic or tricyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, and sulfur;
- triaryl silyl;
- R5 is halogen;
- each R6 is independently a neutral ligand, preferably selected from an ether, a nitrile, a pyridine, an amine, and a phosphine;
- and
- n is 0-2;
- wherein
- each of R1, R4, or C1-20 aliphatic, C1-20 heteroaliphatic or aryl as defined for R2 and R3 may be independently substituted with one or more of halogen, or R′, —OR′, —SR′ —OSi(R′)3, —N(R′)2, —NR′C(O)R′ or —NR′OR′, wherein
- R′ is independently hydrogen, C1-20 aliphatic, C1-20 heteroaliphatic having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur;
- or a 3-7 membered saturated carbocyclic ring, an 8-10 membered bicyclic saturated ring or aryl ring, a 5-6 membered heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, a 4-7 membered saturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, a 7-10 membered bicyclic saturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, and sulfur, and an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, and sulfur, wherein:
- two R′ groups on the same nitrogen atom are optionally taken together with the nitrogen atom to form an optionally substituted 3-8 membered, saturated ring or aryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur;
- with the proviso that the compound of formula I-a is not
- Mo(NAr*)(CHCMe2Ph)Cl(OAr*)(py);
- Mo(NAr*)(CHCMe2Ph)Cl(O-t-Bu)(py);
- Mo(NAr*)(CHCMe2Ph)Cl[OCMe(CF3)2](py);
- Mo(NAr*)(CHCMe2Ph)Cl(OAr′)(py);
- and the compound of formula I-b is not
- W(O)(CH-t-Bu)Cl(OHIPT)(PMe2Ph);
- W(O)(CH-t-Bu)Cl(OHMT)(PMe2Ph);
- W(O)(CHCMe2Ph)Cl(OHMT)(PMe2Ph);
- W(O)(CHCMe2Ph)Cl(ODFT)(PMe2Ph);
- W(O)(CHCMe2Ph)Cl(OTPP)(PMe2Ph);
- W(O)(CHCMe2Ph)Cl(OdAdP)(PMe2Ph);
- W(O)(CHCMe2Ph)Cl(ODBMP)(PMe2Ph);
- wherein Ar* is 2,6-dimesitylphenyl (HMT);
- Ar′ is 2,6-dimethylphenyl;
- OHIPT is 2,6-(2,4,6-(i-Pr)3C6H2)2C6H3, DFT is 2,6-di(pentafluorophenyl)phenyl;
- TPP is 2,3,5,6-tetraphenylphenyl;
- dAdP is 2,6-diadamantylphenyl;
- DBMP is 4-methyl-2,6-di(diphenylmethyl)phenyl;
- Me is methyl;
- Ph is phenyl;
- Bu is butyl;
- and py is pyridine.
49 more elements
A compound of formula I-c:
- wherein:
- M is tungsten;
- R1 is a group selected from adamantyl, t-butyl, and phenyl;
- each of R2 and R3 is independently hydrogen or C(CH3)3 or C(CH3)2C6H5 or phenyl;
- R4 is a group selected from an aryl ring;
- R5 is chlorine or bromine;
- each R6 is independently a neutral ligand selected from a nitrile, a pyridine and a phosphine;
- and
- n is 0-2;
- wherein
- each of phenyl as defined for R1, R2 and R3 and aryl as defined for R4 may be independently substituted with one or more of halogen, or R′, —OR′, —SR′—OSi(R′)3, —N(R′)2, —NR′C(O)R′ or —NR′OR′, wherein
- R′ is independently hydrogen, C1-20 aliphatic, C1-20 heteroaliphatic having 1-3 heteroatoms independently selected from nitrogen and oxygen, a 5-6 membered saturated carbocyclic ring, an 8-10 membered bicyclic saturated ring or aryl ring, a 5-6 membered heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, a 4-7 membered saturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, and sulfur, and an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, and sulfur, wherein:
- two R′ groups on the same nitrogen atom are optionally taken together with the nitrogen atom to form an optionally substituted 3-8 membered, saturated ring or aryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur;
- with the proviso that the compound of formula I-c is not W(N-t-Bu)(CH-t-Bu)Cl(OHMT)(py);
- wherein HMT is 2,6-dimesitylphenyl and py is pyridine.
12 more elements
Dependencies are inferred from the claim text.