IP Library Granted Patent US 9,597,674
Granted Patent B2
US 9,597,674 · App. 13/978,940 · Granted Mar 21, 2017

Z-selective olefin metathesis catalysts and their synthetic procedure

Inventors: Koji Endo (Chiba, JP); Benjamin Keith Keitz (Pasadena, CA); Myles Benton Herbert (Pasadena, CA); Paresma Rasiklal Patel (Los Angeles, CA); Robert Howard Grubbs (Pasadena, CA)
Assignee: CALIFORNIA INSTITUTE OF TECHNOLOGY
B01J31/2295B01J31/2208B01J31/2273B01J31/2278C07C6/04C07C67/343C07F15/0046B01J31/223B01J31/2226B01J2231/543B01J2531/0261B01J2531/821C07C2531/22Y02P20/52
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Quick Facts
Patent No.
US 9,597,674
App. No.
13/978,940
Granted
Mar 21, 2017
Kind
B2
Abstract

The invention relates to C—H activated olefin metathesis catalyst compounds, the preparation of such compounds, and the use of such catalysts in the metathesis of olefins and olefin compounds, more particularly, the use of such catalysts in Z selective olefin metathesis reactions. In general, the catalyst compounds of the invention comprise a Group 8 metal (M), an alkylidene moiety (═CR 1 R 2 ), or more generally (═(C) m CR 1 R 2 ), an anionic ligand (X 1 ), two or three neutral ligands (L 1 , L 2 , and L 3 ) and a 2-electron anionic donor bridging moiety (Q*) that forms a chelate ring structure in conjunction with L1 and M. Such catalysts generally correspond to the formula X 1 (L 3 ) k L 2 L 1 Q*M=(C) m CR 1 R 2 , wherein X1 is any anionic ligand, L 1 , L 2 , and L 3 are, independently, any neural electron donor ligand, k is 0 or 1, m is 0, 1, or 2, Q* is a 2-electron anionic donor bridging moiety linking L 1 and M, M is a Group 8 transition metal, and R 1 and R 2 are, independently, hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or functional groups. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemicals chemistry.

Claims (14)

1. A C—H activated olefin metathesis catalyst compound, wherein the compound has the structure of formula (VIII):

wherein,

Q is hydrocarbylene, or alkyl substituted hydrocarbylene;

Q* forms a carbon-Ruthenium bond with the carbon from the R 3 group;

X 1 is nitrate, or C 1 -C 20 alkylcarboxylate;

R 3 is a cycloalkyl or an alkyl substituted cycloalkyl group;

R 4 is an alkyl substituted aryl group;

Z is alkyl; and

R 5 , R 6 , R 7 and R 8 are hydrogen.

2. The compound of claim 1 , wherein

Q is selected from: —CH 2 —CH 2 —, —C(Me) 2 — and —CH 2 —C(Me) 2 —; and

R 3 is an adamantyl or an alkyl substituted adamantyl group, or an alkyl substituted C 3 -C 12 cycloalkyl group.

3. The compound of claim 2 , wherein R 4 is an alkyl substituted aryl group in which both ortho ring positions are substituted.

4. The compound of claim 2 , selected from

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 6, 2014
From: ENDO, KOJI; KEITZ, BENJAMIN KEITH; HERBERT, MYLES BENTON; PATEL, PARESMA RASIKLAL; GRUBBS, ROBERT HOWARD
To: CALIFORNIA INSTITUTE OF TECHNOLOGY
Reel/Frame 031895/0443 →
CONFIRMATORY LICENSE Recorded Aug 23, 2013
From: CALIFORNIA INSTITUTE OF TECHNOLOGY
To: NATIONAL INSTITUTES OF HEALTH (NIH), U.S. DEPT. OF HEALTH AND HUMAN SERVICES (DHHS), U.S. GOVERNMENT
Reel/Frame 031076/0152 →
Continuity (4)
Provisional Application 61432849 · Jan 14, 2011
Provisional Application 61433949 · Jan 18, 2011
Provisional Application 61515262 · Aug 4, 2011
Related Publication 20140106960A1 · Apr 17, 2014