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

Patent metadata

Field	Value
Publication number	US-9687834-B2
Application number	US-86426109-A
Country	US
Kind code	B2
Filing date	Jan 23, 2009
Priority date	Jan 25, 2008
Publication date	Jun 27, 2017
Grant date	Jun 27, 2017

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. A composition, comprising: 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;
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; 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.

2. A composition, comprising: 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 croup of the chiral biaryl croup coordinates the metal atom M, and wherein the hydroxyl group is deprotonated upon coordination to the metal center.

3. The composition of claim 1 , 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.

4. The composition of claim 1 , 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.

5. The composition of claim 1 , 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.

6. A composition, comprising:
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

R 17 can be the same or different and is hydrogen, halogen, alkyl, heteroalkyl, aryl, acyl, or —OP, optionally substituted;
R 2 is CMe 2 Ph or CMe 3 ;
R 3 is hydrogen;
R 4 is an enantiomer of the following structure,

wherein each R 7 and R 10 is the same or different and is halogen, methyl, t-butyl, CF 3 , or aryl, optionally substituted; and TBS is tert-butyldimethylsilyl;
wherein said hydroxyl group of said enantiomer R 4 coordinates the metal atom M, and wherein the hydroxyl group is deprotonated upon coordination to the metal center;
R 5 is

wherein 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.

7. The composition of claim 6 , wherein:
M=Mo
R 7 ═R 10 selected from halogen, methyl
R 5 =

8. The composition of claim 6 , wherein the metal complex has the structure,

wherein R 19 is F, Cl, Br, or I.

9. The composition of claim 2 , wherein R 7 and R 10 are the same or different and are selected from the group consisting of F, Cl, Br, or I.

10. The composition of claim 1 , wherein M is Mo.

11. The composition of claim 2 , wherein R 1 is

wherein each R 17 can be the same or different and is hydrogen, halogen, alkyl, heteroalkyl, aryl, acyl, or —

Assignees

• Malcolmson Steven J
• Hoveyda Amir H
• Meek Simon J
• Schrock Richard R
• Trustees Boston College
• Massachusetts Inst Technology

Inventors

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

Classifications

• B01J31/2208

  Oxygen, e.g. acetylacetonates · CPC title

• B01J2531/64

  Molybdenum · CPC title

• B01J2231/54

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

• B01J31/1805 Primary

  the ligands containing nitrogen · CPC title

• B01J31/2265

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