Biaryl ligands, methods of making biarlyl ligands, and methods of use thereof

Patent metadata

Field	Value
Publication number	US-11198701-B2
Application number	US-202016792794-A
Country	US
Kind code	B2
Filing date	Feb 17, 2020
Priority date	Sep 13, 2013
Publication date	Dec 14, 2021
Grant date	Dec 14, 2021

Abstract

Embodiments of the present disclosure provide for biaryl ligands (also referred to herein as “biaryl compound”), biaryl complexes, methods of making biaryl compounds, methods of making single enantiomers of these biaryl compounds, methods of use (e.g., catalysis), and the like.

First claim

The invention claimed is:

1. A method of making a biaryl compound, comprising:

wherein the biaryl product has the following structure:

wherein each of the R 5 groups is independently selected from the group consisting of: hydrogen, a halogen group, a 3 to 10 carbon atom cyclic alkyl group, a 1 to 20 carbon atom linear alkyl group, an aryl group, a —OR group, a —SR group, a —SiR (3) group, a NR (2) cyclic group, and a NR (2) linear group, wherein each R is independently selected from the group consisting of: hydrogen, a 3 to 10 carbon atom cyclic alkyl group, a 1 to 20 carbon atom linear alkyl group, and an aryl group, wherein n is 1 to 5, wherein X is C or S, wherein each R 6 and R 7 group is independently selected from the group consisting of: hydrogen, a 3 to 10 carbon atom cyclic alkyl group, a 1 to 20 carbon atom linear alkyl group, and an aryl group,
wherein X1 is Cl, Br, or I and wherein Y is C, N, O, or S,
wherein R 1 group and R 2 group are independently selected from the group consisting of: hydrogen, a halogen group, a 3 to 10 carbon atom cyclic alkyl group, a 1 to 20 carbon atom linear alkyl group, an aryl group, a —OR group, a —SR group, a —SiR (3) group, a NR (2) cyclic, and NR (2) linear group,
wherein each of the R 4 groups is independently selected from the group consisting of: hydrogen, a halogen group, a 3 to 10 carbon atom cyclic alkyl group, a 1 to 20 carbon atom linear alkyl group, an aryl group, a —OR group, a —SR group, a —SiR (3) group, a NR (2) cyclic group, and a NR (2) linear group, wherein m is 1 to 5, wherein each of the R 3 groups is independently selected from: hydrogen, a 3 to 10 carbon atom cyclic alkyl group, a 1 to 20 carbon atom linear alkyl group, an alkoxide, a phenoxide, an aryl group, and an amine,
wherein DME is dimethoxyethan, TBS is tert-butyldimethylsilyl group, Tf is triflate group, DMAP is 4-dimethylaminopyridine.

2. A method of forming a compound, comprising:

wherein F 5 represents a F attached to each of the 5 carbons of the ring, wherein TBS is tert-butyldimethylsilyl group.

3. A method of forming a compound, comprising:

wherein F 5 represents a F attached to each of the 5 carbons of the ring.

4. A method of using a biaryl compound, comprising:
using a biaryl compound as a catalyst in a reaction selected from one of the following: an enantioselective transformation, an alkyne addition asymmetric allylic alkylation, and an addition to an aliphatic or an aromatic aldehyde, wherein the biaryl compound has the following structure:

wherein each of the R 5 groups is independently selected from: hydrogen, a halogen group, a cyclic or linear, alkyl group, an aryl group, a —OR group, a —SR group, a —SiR (3) group, a NR (2) cyclic or linear group, wherein each R is independently selected from: hydrogen, a cyclic or linear, alkyl group, or an aryl group, wherein n is 1 to 5, wherein X is C or S, wherein each R 6 and R 7 group is independently selected from: hydrogen, a cyclic or linear, alkyl group, an aryl group,
wherein R 1 group and R 2 group are independently selected from: hydrogen, a halogen group, a cyclic or linear, alkyl group, an aryl group, a —OR group, a —SR group, a —SiR (3) group, a NR (2) cyclic or linear group,
wherein each of the R 4 groups is independently selected from: hydrogen, a halogen group, a cyclic or linear, alkyl group, an aryl group, a —OR group, a —SR group, a —SiR (3) group, a NR (2) cyclic or linear group, wherein m is 1 to 5, wherein each of the R 3 groups is independently selected from: hydrogen, a cyclic or linear, alkyl group, an alkoxide, a phenoxide, an aryl group, or a substituted amine.

5. A method comprising:

wherein compound 7 is

wherein F 5 represents a F attached to each of the 5 carbons of the ring, and wherein R is selected from SiMe 3 and Ph.

6. A method, comprising:

wherein compound rac-7 is

wherein F 5 represents a F attached to each of the 5 carbons of the ring, wherein TMS is a trimethylsilyl group.

7. A method, comprising:

wherein compound 7 is

wherein F 5 represents a F attached to each of the 5 carbons of the ring, wherein R is selected from the group consisting of H, OMe, and CF 3 .

8. A method comprising:

wherein aldehyde 1 is

and product 1 is

or
wherein aldehyde 2 is

and product 2 is

or
wherein aldehyde 3 is

and product 3 is

or
wherein aldehyde 4 is

and product 4 is

or
wherein aldehyde 5 is

and product 5 is

or
wherein aldehyde 6 is

and product 6 is

or
wherein aldehyde 7 is

and product 7 is

or
wherein aldehyde 8 is

and product 8 is

and
wherein compound 7 is

Assignees

• Univ Florida

Inventors

• Aponick Aaron
• Cardoso Flavio S P

Classifications

• C07D233/20 Primary

  with substituted hydrocarbon radicals, directly attached to ring carbon atoms · CPC title

• C07D211/74

  Oxygen atoms · CPC title

• B01J31/2447

  and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring · CPC title

• C07F7/083

  Syntheses without formation of a Si-C bond · CPC title

• B01J2231/766

  of -CH-CH- or -C=C- to -C=C- or -C-C- triple bond species · CPC title