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

Patent metadata

Field	Value
Publication number	US-10258976-B2
Application number	US-201615780942-A
Country	US
Kind code	B2
Filing date	Dec 15, 2016
Priority date	Dec 15, 2015
Publication date	Apr 16, 2019
Grant date	Apr 16, 2019

Abstract

Precatalysts of formula I and IV, and processes for the functionalization of SP2-carbons using the same are described herein. The precatalysts comprise a fluoroborate salt protected intramolecular frustrated lewis pair (FLP). The precatalysts are bench stable with improved stability towards moisture and/or air. The precatalysts can be used to generate in situ the corresponding FLP catalyst.

First claim

The invention claimed is:

1. A precatalyst for the functionalization of a sp 2 -carbon, the precatalyst having the structure defined by Formula I:

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;
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;
R 9 is hydrogen, halogen, C 1-15 alkyl, C 3-15 branched alkyl, aryl, OCF 3 , CF 3 , OR 5 or SR 6 ;
wherein when R 9 is present more than once, each R 9 is independently hydrogen, halogen, C 1-15 alkyl, C 3-15 branched alkyl, aryl, OCF 3 , CF 3 , OR 5 or SR 6 ; and
n is an integer ranging from 1 to 4.

2. The precatalyst of claim 1 ,
wherein:
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.

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

wherein:
R 10 is F or OR 11 ; and
R 11 is H, C 1-15 alkyl or C 3-15 branched alkyl.

4. The precatalyst of claim 3 , having the Formula:

5. The precatalyst of claim 3 , having the Formula:

6. The precatalyst of claim 3 , having the Formula:

7. The precatalyst of claim 1 , having the Formula:

8. The precatalyst of claim 1 , having the Formula:

9. The precatalyst of claim 1 , having the Formula:

10. The precatalyst of claim 1 , having a structure defined by Formula III:

wherein
R 12 is H, halogen, C 1-15 alkyl, C 3-15 branched alkyl, aryl, OCF 3 , CF 3 , OR 5 or SR 6 ; and
R 5 and R 6 are independently hydrogen, C 1-15 alkyl or C 3-15 branched alkyl.

11. The precatalyst of claim 10 , having the Formula:

12. A catalytic process for the functionalization of a sp 2 carbon, the process comprising:
contacting a precatalyst as defined in claim 1 ; a functionalization reagent; and a substrate comprising a sp 2 —H carbon, under conditions to provide a substrate comprising a functionalized sp 2 carbon.

13. The catalytic process of claim 12 , wherein the substrate is an alkene, an arene or a heteroarene.

14. The catalytic process of claim 12 , wherein the functionalization reagent is an organoborane reagent.

15. The catalytic process of claim 14 , wherein the organoborane reagent is HBPin, HBCat or 9BBN.

16. The catalytic process of claim 12 , wherein the precatalyst is present from about 1 mol % to about 20 mol %.

17. A catalytic process for the dehydrogenative functionalization of a sp 2 carbon, the process comprising:
contacting a precatalyst as defined in claim 1 ; a functionalization reagent; and a substrate comprising a sp 2 —H carbon, under conditions to provide a substrate comprising a functionalized sp 2 carbon.

18. The catalytic process of claim 17 , wherein the substrate is an alkene, an arene or a heteroarene.

19. The catalytic process of claim 17 , wherein the functionalization reagent is an organoborane reagent.

20. The catalytic process of claim 19 , wherein the organoborane reagent is HBPin, HBCat or 9BBN.

21. The catalytic process of claim 17 , wherein the precatalyst is present from about 1 mol % to about 20 mol %.

Assignees

• Univ Laval

Inventors

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

Classifications

• C07F5/025

  Boronic and borinic acid compounds · CPC title

• C07F5/027

  Organoboranes and organoborohydrides · CPC title

• B01J31/146 Primary

  of boron · CPC title

• C07F5/02

  Boron compounds · CPC title

• B01J31/0231

  Halogen-containing compounds · CPC title