Catalysts for metathesis reactions including enantioselective olefin metathesis, and related methods

Patent metadata

Field	Value
Publication number	US-2017333887-A1
Application number	US-201715615644-A
Country	US
Kind code	A1
Filing date	Jun 6, 2017
Priority date	Jan 25, 2008
Publication date	Nov 23, 2017
Grant date	—

Abstract

The present invention provides compositions comprising metal complexes, and related methods. In some embodiments, metal complexes of the invention may be useful as catalysts for chemical reactions, including metathesis reactions, wherein the catalysts exhibit enhanced activity and stereoselectivity. In some embodiments, the invention may advantageously provide metal complexes comprising a stereogenic metal atom. Such metal complexes may be useful in enantioselective catalysis.

First claim

What is claimed:

1 - 24 . (canceled)

25 . A method, comprising:
reacting a first species comprising an olefin and a second species comprising an olefin via a cross-metathesis reaction to produce a product comprising a double bond, the double bond comprising an atom of the first species and an atom of the second species, wherein the double bond is produced in a Z:E ratio greater than about 1:1 in favor of the Z-isomer, and wherein the reaction between the first species and the second species is catalyzed by a metal complex comprising a stereogenic metal atom and two or more ligands, wherein each ligand associated with the metal complex comprises an organic group and binds the stereogenic metal atom via one site of the ligand, wherein the composition comprises the metal complex in a diastereomeric ratio greater than 1:1; wherein the metal complex has the structure,

wherein:
M is Mo or W;
R 1 is aryl or alkyl, optionally substituted with one or more of R 5 ;
R 2 is hydrogen, alkyl, or aryl, optionally substituted;
R 3 is alkyl, optionally substituted;
R 4 is a chiral biaryl group, optionally substituted; and
R 5 is alkyl, heteroalkyl, aryl, heteroaryl, halogen, or a silyl group, optionally substituted;
wherein the chiral biaryl group is

wherein R 7 is aryl, heteroaryl, alkyl, or heteroalkyl, optionally substituted;
R 8 is OP;
R 9 is —OH;
is hydrogen, halogen, alkyl, heteroalkyl, aryl, heteroaryl, or acyl, optionally substituted;
each R 11 , R 12 , R 13 , and R 14 can be the same or different and is aryl, heteroaryl, alkyl, heteroalkyl, or acyl, optionally substituted; or,
together R 11 and R 12 are joined to form a ring, optionally substituted; or
together R 13 and R 14 are joined to form a ring, optionally substituted; and
P is a protecting group;
wherein R 4 coordinates the metal atom M via the hydroxyl group R 9 of the chiral biaryl group, and
wherein the hydroxyl group is deprotonated upon coordination to the metal center.

26 - 31 . (canceled)

32 . The method of claim 25 , wherein the catalyzing occurs with an enantiomeric excess greater than 50%.

33 - 37 . (canceled)

38 . The method of claim 25 , wherein the catalyzing or reacting occurs with a yield of at least 50%.

39 - 47 . (canceled)

48 . The method of claim 25 , wherein the catalyst is present in the cross-metathesis reaction in an amount of 10 mol % or less.

49 - 80 . (canceled)

81 . The method of claim 25 , wherein the cross-metathesis reaction is conducted under an atmosphere of ethylene.

82 - 86 . (canceled)

87 . The method of claim 25 , wherein R 1 is

wherein each R 17 can be the same or different and is hydrogen, halogen, alkyl, heteroalkyl, aryl, acyl, or —OP, optionally substituted;
and P is a protecting group.

88 . The method of claim 25 , wherein R 1 is

wherein each R 17 can be the same or different and is hydrogen, halogen, alkyl, heteroalkyl, aryl, acyl, or —OP, optionally substituted; and
P is a protecting group.

89 . The method of claim 25 , wherein R 5 is

wherein each R 6 can be the same or different and is hydrogen, alkyl, heteroalkyl, aryl, heteroaryl, and X may be present or absent and is methyl, ethyl or a protecting group.

90 . The method of claim 25 , wherein M is Mo.

91 . A method, comprising:
reacting a first species comprising an olefin and a second species comprising an olefin via a cross-metathesis reaction to produce a product comprising a double bond, the double bond comprising an atom of the first species and an atom of the second species, wherein the double bond is produced in a Z:E ratio greater than about 1:1 in favor of the Z-isomer, and wherein the reaction between the first species and the second species is catalyzed by a metal complex comprising a stereogenic metal atom and two or more ligands, wherein each ligand associated with the metal complex comprises an organic group and binds the stereogenic metal atom via one site of the ligand, wherein the composition comprises the metal complex in a diastereomeric ratio greater than 1:1; wherein the metal complex has the structure,

wherein:
M is Mo or W;
R 1 is aryl or alkyl, optionally substituted with one or more of R 5 ;
R 2 is hydrogen, alkyl, or aryl, optionally substituted;
R 3 is alkyl, optionally substituted;
R 4 is a chiral biaryl group, optionally substituted; and
R 5 is alkyl, heteroalkyl, aryl, heteroaryl, halogen, or a silyl group, optionally substituted;
wherein the chiral biaryl group is a hydroxyl-containing chiral biaryl group and is selected from

wherein each R 7 and R 8 can be the same or different and is hydrogen, halogen, alkyl, alkoxy, aryl, CF 3 , —OSi-tri-alkyl, —OSi-tri-aryl, —OSi-alkyl-diphenyl, —OSi-phenyl-dialkyl, or acyl;
R 10 is hydrogen, halogen, alkyl, heteroalkyl, aryl, heteroaryl, or acyl, optionally substituted;
each R 11 , R 12 , R 13 , and R 14 can be the same or different and is aryl, heteroaryl, alkyl, heteroalkyl, or acyl, optionally substituted; or, together R 11 and R 12 are joined to form a ring, optionally substituted; or, together R 13 and R 14 are joined to form a ring, optionally substituted;
R 15 is alkyl, aryl, —Si-trialkyl, —Si-triaryl, —Si-alkyldiphenyl, —Si-phenyldialkyl, or acyl;
X can be methyl, ethyl or a protecting group;
each Z can be the same or different and is (CH 2 ) m , N, O, optionally substituted;
n is 0-5; and m is 1-4;
wherein said hydroxyl group of the chiral biaryl group coordinates the metal atom M, and wherein the hydroxyl group is deprotonated upon coordination to the metal center.

92 . The method of claim 91 , wherein R 7 and R 10 are the same or different and are selected from the group consisting of F, Cl, Br, or I.

93 . The method of claim 91 , wherein R 1 is

wherein each R 17 can be the same or different and is hydrogen, halogen, alkyl, heteroalkyl, aryl, acyl, or —OP, optionally substituted; and
P is a protecting group.

94 . The method of claim 91 , wherein R 1 is

wherein each R 17 can be the same or different and is hydrogen, halogen, alkyl, heteroalkyl, aryl, acyl, or —OP, optionally substituted; and
P is a protecting group.

95 . The method of claim 91 , wherein R 5 is

Assignees

• Trustees Boston College
• Massachusetts Inst Technology

Inventors

• Malcolmson Steven J
• Hoveyda Amir H
• Meek Simon J
• Schrock Richard R

Classifications

• B01J2231/54

  Metathesis reactions, e.g. olefin metathesis · CPC title

• B01J31/2265

  Carbenes or carbynes, i.e.(image) · CPC title

• B01J31/2208

  Oxygen, e.g. acetylacetonates · CPC title

• C07F11/005

  compounds without a metal-carbon linkage · CPC title

• B01J31/1805 Primary

  the ligands containing nitrogen · CPC title