Process for the functionalization of sp2-H carbons using frustrated lewis pair catalysts

Patent metadata

Field	Value
Publication number	US-10988488-B2
Application number	US-201615567662-A
Country	US
Kind code	B2
Filing date	Apr 21, 2016
Priority date	Apr 23, 2015
Publication date	Apr 27, 2021
Grant date	Apr 27, 2021

Abstract

A catalytic process for the metal-free functionalization of sp 2 -carbons is described herein. The catalytic process is suitable for forming borylated alkenes, arenes and heteroarenes and comprises the use of catalysts comprising a Frustrated Lewis Pair (FLP).

First claim

The invention claimed is:

1. A catalytic process for the functionalization of a sp 2 carbon, the process comprising:
contacting a compound of Formula I:

wherein:
A is N;
M is B;
R 1 and R 2 are independently hydrogen, C 1-15 alkyl, C 4-15 branched alkyl, C 6-18 aryl, C 6-18 aryl having at least one C 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 may further comprise at least one heteroatom selected from nitrogen, oxygen and sulfur, and wherein the nitrogen containing ring system 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 4-15 branched alkyl, C 6-18 aryl, C 6-18 aryl having at least one substituent chosen from halogen and C 1-10 alkyl, C 5-8 cycloalkyl;
C 5-8 cycloalkyl having at least one C 1-10 alkyl substituent, OR 6 ; or
R 3 and R 4 are linked together to form a boron containing ring system, wherein the boron containing ring system may further comprise at least one heteroatom selected from nitrogen, oxygen and sulfur, and wherein the boron containing ring system is optionally substituted by one or more C 1-10 alkyl groups;
R 5 is hydrogen, C 1-15 alkyl, OR 6 , and halogen;
R 6 is C 1-15 alkyl;
L is a heteroarene, arene, or a carbon chain (C 1 trough C 20 ) which can be linear, cyclic or branched and may comprise heteroatoms, with the proviso that A and M are in a vicinal position relative to each other; or
L is a polymer comprising monomeric repeating units having an aryl group, with the proviso that A and M are in a vicinal position relative to each other on the aryl groups;
a functionalization reagent; and
a substrate comprising a sp 2 -H carbon;

under conditions to provide a substrate comprising a functionalized sp 2 carbon; wherein the functionalization reagent is an organoborane reagent.

2. The catalytic process of claim 1 , wherein A is N, M is B and L is C 6 aryl.

3. The catalytic process of claim 1 , wherein the substrate is an alkene, an arene or a heteroarene.

4. The catalytic process of claim 1 , wherein the substrate is N-methylpyrrole, N-benzylpyrrole, 1-(trimethylsilyl)pyrrole, 1-(triisopropylsilyl)pyrrole, 1-methylindole, 3,4-ethylenedioxythiophene, 2-methoxythiophene, furan, 2-methylfuran, 2-t-butylfuran, 2-methoxyfuran, 2-trimethylsiloxyfuran, 3-bromofuran, 2-bromofuran and thiophene.

5. The catalytic process of claim 1 , wherein the organoborane reagent is chosen from HBPin, HBCat and 9BBN.

6. The catalytic process of claim 1 , further characterized by the absence of metal based or organometallic reagents.

7. The catalytic process of claim 1 , further characterized by heating in a suitable solvent at temperatures ranging from 60 to 120° C.

8. The catalytic process of claim 1 , wherein the compound of Formula I is present from about 1 mol % to about 10 mol %.

9. A catalytic process for the dehydrogenative functionalization of a sp 2 carbon, the process comprising:
contacting a compound of Formula I:

wherein:
A is N;
M is B;
R 1 and R 2 are independently hydrogen, C 1-15 alkyl, C 4-15 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 may further comprise at least one heteroatom selected from nitrogen, oxygen and sulfur, and wherein the nitrogen containing ring system 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 4-15 branched alkyl, C 6-18 aryl, C 6-18 aryl having at least one substituent chosen from halogen and C 1-10 alkyl, C 5-8 cycloalkyl;
C 5-8 cycloalkyl having at least one C 1-10 alkyl substituent, OR 6 ; or
R 3 and R 4 are linked together to form a boron containing ring system, wherein the boron containing ring system may further comprise at least one heteroatom selected from nitrogen, oxygen and sulfur, and wherein the boron containing ring system is optionally substituted by one or more C 1-10 alkyl groups;
R 5 is hydrogen, C 1-15 alkyl, OR 6 , and halogen;
R 6 is C 1-15 alkyl;
L is a heteroarene, arene, or a carbon chain (C 1 trough C 20 ) which can be linear, cyclic or branched and may comprise heteroatoms, with the proviso that A and M are in a vicinal position relative to each other; or
L is a polymer comprising monomeric repeating units having an aryl group, with the proviso that A and M are in a vicinal position relative to each other on the aryl groups;
a functionalization reagent; and
a substrate comprising a sp 2 -H carbon;

under conditions to provide a substrate comprising a functionalized sp 2 carbon; wherein the functionalization reagent is an organoborane reagent.

10. The catalytic process of claim 9 , wherein A is N, M is B and L is C 6 aryl.

11. The catalytic process of claim 9 , wherein the substrate is an alkene, an arene or a heteroarene.

12. The catalytic process of claim 9 , wherein the substrate is N-methylpyrrole, N-benzylpyrrole, 1-(trimethylsilyl)pyrrole, 1-(triisopropylsilyl)pyrrole, 1-methylindole, 3,4-ethylenedioxythiophene, 2-methoxythiophene, furan, 2-methylfuran, 2-t-butylfuran, 2-methoxyfuran, 2-trimethylsiloxyfuran, 3-bromofuran, 2-bromofuran and thiophene.

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

14. The catalytic process of claim 9 , further characterized by the absence of metal based or organometallic reagents.

15. The catalytic process of claim 9 , further characterized by heating in a suitable solvent at temperatures ranging from 60 to 120° C.

16. The catalytic process of claim 9 , wherein the compound of Formula I is present from about 1 mol % to about 10 mol %.

17. The catalytic process of claim 1 , wherein the compound of Formula I is:

18. The catalytic process of claim 9 , wherein the compound of Formula I is:

Assignees

• Univ Laval

Inventors

• Fontaine Frederic-Georges
• Legare Marc-Andre
• Courtemanche Marc-Andre

Classifications

• B01J2231/4277

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

• B01J31/0272

  containing elements other than those covered by B01J31/0201 - B01J31/0255 · CPC title

• C07F5/025

  Boronic and borinic acid compounds · CPC title

• C07F5/027 Primary

  Organoboranes and organoborohydrides · CPC title

• B01J31/146

  of boron · CPC title