Highly Z-selective olefin metathesis

Patent metadata

Field	Value
Publication number	US-10173208-B2
Application number	US-201715399485-A
Country	US
Kind code	B2
Filing date	Jan 5, 2017
Priority date	Sep 30, 2009
Publication date	Jan 8, 2019
Grant date	Jan 8, 2019

Abstract

The present invention relates generally to catalysts and processes for the Z-selective formation of internal olefin(s) from terminal olefin(s) via homo-metathesis reactions.

First claim

What is claimed:

1. A method comprising:
providing a catalyst having the structure:

wherein M is Mo or W;
R 1 is aryl, heteroaryl, alkyl, heteroalkyl, optionally substituted;
R 2 and R 3 can be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl, optionally substituted; and
R 4 and R 5 can be the same or different and are alkyl, heteroalkyl, aryl, heteroaryl, silylalkyl, or silyloxy, optionally substituted, wherein at least one of R 4 or R 5 is a ligand containing oxygen bound to M; and

reacting a first molecule comprising a terminal double bond with a second molecule that comprises a terminal double bond in the presence of the catalyst to produce a product comprising an internal double bond, and
wherein the internal double bond of the product comprises one carbon atom from the terminal bond of the first molecule and one carbon atom from the terminal double bond of the second molecule.

2. The method of claim 1 , wherein the first molecule and the second molecule are identical.

3. The method of claim 1 , wherein at least about 30% of the internal double bond of the product is formed as the Z-isomer.

4. The method of claim 1 , wherein the reaction proceeds with a conversion of at least about 30%.

5. The method of claim 1 , wherein at least one of the first and second molecules has the formula:

wherein R a is H, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, heteroaryl, or acyl, optionally substituted.

6. The method of claim 1 , wherein one of R 4 and R 5 is a ligand containing oxygen bound to M, optionally substituted, and the other is a ligand containing nitrogen bound to M, optionally substituted.

7. The method of claim 6 , wherein the at least one ligand containing oxygen bound to M lacks a plane of symmetry.

8. The method of claim 6 , wherein the ligand containing nitrogen bound to M is selected from the group consisting of pyrrolyl, pyrazolyl, pyridinyl, pyrazinyl, pyrimidinyl, imidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, indolyl, indazolyl, carbazolyl, morpholinyl, piperidinyl, and oxazinyl, all optionally substituted.

9. The method of claim 6 , wherein the ligand containing oxygen bound to M comprises a group having the formula —OSi(R 22 ) 3 , wherein each R 22 can be the same or different and is aryl or alkyl, optionally substituted.

10. The method of claim 6 , wherein the ligand containing nitrogen bound to M has the structure:

wherein each R 6 can be the same or different and is hydrogen, alkyl, heteroalkyl, aryl, or heteroaryl, optionally substituted; and
X may be present or absent and is any non-interfering group.

11. The method of claim 6 , wherein the ligand containing oxygen bound to M has the following structure:

wherein R 7 is aryl, heteroaryl, alkyl, or heteroalkyl, optionally substituted;
R 8 is

hydrogen, —OH, halogen, alkyl, heteroalkyl, aryl, heteroaryl, acyl, acyloxy, or —OP, optionally substituted; or,
together R 7 and R 8 are joined to form a ring, optionally substituted;
R 9 is

when R 8 is not

or —OH, —OP, or amino, optionally substituted;
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.

12. The method of claim 6 , wherein R 4 is a derivative of the following structure:

wherein P is a silyl protecting group.

13. The method 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.

14. The method 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.

15. The method 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;
R 2 is CMe 2 Ph or CMe 3 ;
R 3 is H; and
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
P is a protecting group.

16. The method of claim 15 , wherein R 5 has the following structure:

wherein each R 6 can be the same or different and is hydrogen, alkyl, heteroalkyl, aryl, heteroaryl, optionally substituted; and
X may be present or absent and is any non-interfering group.

17. The method of claim 6 , wherein the ligand containing oxygen or nitrogen bound to M has the following structure:

wherein each R 7 and R 8 can be the same or different and is hydrogen, halogen, alkyl, alkoxy, aryl, acyl, or a protecting group, optionally substituted;
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, or a protection group, optionally substituted;
R 16 is hydrogen or an amine protecting group;
X can be any non-interfering group;

Assignees

• Massachusetts Inst Technology
• Trustees Boston College

Inventors

• Schrock Richard R
• King Annie J
• Zhao Yu
• Flook Margaret M
• Hoveyda Amir H

Classifications

• B01J31/181

  Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine · CPC title

• C07C2531/18

  containing nitrogen, phosphorus, arsenic or antimony · CPC title

• C07F11/00

  Compounds containing elements of Groups 6 or 16 of the Periodic Table · CPC title

• C07C2602/10

  the other ring being six-membered, e.g. tetraline · CPC title

• C07C67/475

  by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of [IMAGE cpc-sch-C07C-0963.gif] groups between different molecules · CPC title