Precatalysts and process for the metal-free functionalization of SP2 carbons using the same

Patent metadata

Field	Value
Publication number	US-10821429-B2
Application number	US-201916291948-A
Country	US
Kind code	B2
Filing date	Mar 4, 2019
Priority date	Dec 15, 2015
Publication date	Nov 3, 2020
Grant date	Nov 3, 2020

Abstract

Precatalysts and catalytic processes for the functionalization of sp2-carbons using the precatalysts are described herein. The precatalysts comprise an intramolecular Frustrated Lewis Pair (FLP) that is generated in situ from the corresponding precatalyst fluoroborate salts. The precatalyst fluoroborate salts are deprotected in situ to generate catalysts including intramolecular FLPs for the dehydrogenative borylation of alkenes, arenes and heteroarenes. The catalytic process comprises contacting a precatalyst, a functionalization reagent; and a substrate comprising a sp2-H carbon, under conditions to provide a substrate comprising a functionalized sp2 carbon.

First claim

The invention claimed is:

1. A precatalyst for the functionalization of a sp a -carbon, the precatalyst having a structure defined by the Formula P1:

wherein:
R 1 and R 2 are independently, C 1-15 alkyl, C 3-15 branched alkyl, C 6-18 aryl, C 6-18 aryl having at least one C 1-10 alkyl substituent, C 5-8 cycloalkyl, C 5-8 cycloalkyl having at least one C 1-10 alkyl substituent; or
R 1 and R 2 are linked together to form a nitrogen containing ring system, wherein the nitrogen containing ring system is optionally substituted by one or more C 1-10 alkyl groups; or
R 1 and R 2 are linked together to form a morpholine, piperazine, N′-alkyl piperazine, or thiomorpholine ring system that is optionally substituted by one or more C 1-10 alkyl groups;
R 3 and R 4 are independently hydrogen, halogen, C 1-15 alkyl, C 3-15 branched alkyl, C 6-18 aryl, C 6-18 aryl having at least one C 1-10 alkyl substituent, C 5-8 cycloalkyl, C 5-8 cycloalkyl having at least one C 1-10 alkyl substituent, OR 5 , SR 6 ; or
R 3 and R 4 are linked together to form a boron containing ring system, wherein the boron containing ring system is optionally substituted by one or more C 1-10 alkyl groups;
R 5 and R 6 are independently hydrogen, C 1-15 alkyl or C 3-15 branched alkyl; and
n is an integer ranging from 10 to 1000.

2. The precatalyst of claim 1 , having a structure defined by Formula PIa:

wherein n is an integer ranging from 10 to 1000.

3. The precatalyst of claim 1 , having a structure defined by Formula PIb:

wherein n is an integer ranging from 10 to 1000.

4. The precatalyst of claim 1 , having a structure defined by Formula PIc:

wherein n is an integer ranging from 10 to 1000.

5. A catalytic process for the functionalization of a sp 2 carbon, the process comprising:
contacting a precatalyst as defined in claim 1 with a functionalization reagent and a substrate comprising a sp 2 -H carbon, under conditions to functionalize the sp 2 -H carbon on the substrate.

6. The catalytic process of claim 5 , wherein the substrate is an alkene, an arene or a heteroarene.

7. The catalytic process of claim 5 , wherein the functionalization reagent is an organoborane reagent.

8. The catalytic process of claim 7 , wherein the organoborane reagent is HBPin, HBCat or 9BBN.

9. The catalytic process of claim 5 , wherein the precatalyst is present from about 1 mol % to about 20 mol %.

10. The catalytic process of claim 9 , wherein the precatalyst is present from about 1 mol % to about 15 mol %.

11. The catalytic process of claim 10 , wherein the precatalyst is present from about 1 mol % to about 10 mol %.

12. The catalytic process of claim 11 , wherein the precatalyst is present from about 1 mol % to about 5 mol %.

13. The catalytic process of claim 5 , wherein the functionalization is a dehydrogenative functionalization.

Assignees

• Univ Laval

Inventors

• Fontaine Frédéric-Georges
• Légaré Marc-André
• Rochette Étienne
• Bouchard Nicolas

Classifications

• B01J31/063

  Polymers comprising a characteristic microstructure · CPC title

• B01J2231/4277

  C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues · CPC title

• B01J31/146 Primary

  of boron · CPC title

• C08F12/28 Primary

  Amines · CPC title

• C08L25/18

  Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen · CPC title