Intermolecular C-H silylation of unactivated arenes

Patent metadata

Field	Value
Publication number	US-9938204-B2
Application number	US-201414916787-A
Country	US
Kind code	B2
Filing date	Sep 8, 2014
Priority date	Sep 6, 2013
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

Abstract

Reaction mixtures for silvlating arene substrates and methods of using such reaction mixtures to silyiate the arene substrates are provided. Exemplary reaction mixtures include the arene substrate, a liganded metal catalyst, a hydrogen acceptor and an organic solvent. The reaction conditions allow for diverse substituents on the arene substrate.

First claim

What is claimed is:

1. A reaction mixture for silylating an arene substrate, said reaction mixture comprising:
(i) a substituted arene or heteroarene substrate comprising a silylatable moiety;
(ii) a liganded metal capable of catalyzing said silylating;
(iii) optionally, a hydrogen acceptor; and
(iv) a silicon source of Formula I:

in which R s , R t and R u are independently from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl and XR x , in which X is a heteroatom and R x is H or substituted or unsubstituted alkyl, substituted or unsubstituted aryl or substituted silyl, and one, two or three of, R s , R t and R u is XR x .

2. The reaction mixture according to claim 1 , wherein said arene substrate has the formula:

wherein
R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, halogen, BR 7 R 8 , CN, CF 3 , acyl, —SO 2 NR 7 R 8 , —NR 7 R 8 , —OR 7 ,—S(O) 2 R 7, —C(O)R 7 , —COOR 7 , —CONR 7 R 8 , —S(O) 2 OR 7 , —OC(O)R 7 , —C(O)NR 7 R 8 , —NR 7 C(O)R 8 , —NR 7 SO 2 R 8 and —NO 2 , wherein two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 , together with the atoms to which they are bonded, are optionally joined to form a ring system which is substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl
wherein
R 7 and R 8 are independently H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl and substituted or unsubstituted heterocycloalkyl, and R 7 and R 8 , together with the atoms to which they are bonded, are optionally joined to form a 5- to 7-membered ring which is substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl.

3. The reaction mixture according to claim 1 , wherein said substrate is 1,3-substituted.

4. The reaction mixture according to claim 1 , wherein in said liganded metal, ligand is a phosphorus-containing ligand.

5. The reaction mixture according to claim 1 , wherein in said liganded metal, ligand is a phosphorus-containing ligand, which is a biaryl ligand.

6. The reaction mixture according to claim 1 , wherein in said liganded metal, ligand is a phosphorus-containing ligand, which is a biaryl ligand having the formula:

wherein
R a , R b , R c , R d , R o , R a′ , R b′ , R c′ , R d′ , and R o′ , are each independently H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, halogen, CN, CF 3 , acyl, —SO 2 NR e R f , —OR e , —S(O) 2 R e , —C(O)R e , —COOR e , —CONR e R f , —S(O) 2 OR e , —OC(O)R e , —C(O)NR e R f , —NR e C(O)R f , —NR e SO 2 R f and —NO 2 , wherein two or more of R a , R b , R c , R d , R e , R f , R a′ , R b′ , R c′ , and R d′ , together with the atoms to which they are bonded, are optionally joined to form a ring system which is substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl;
R e and R f include independently H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl and substituted or unsubstituted heterocycloalkyl, and R e and R f , together with the atoms to which they are bonded, are optionally joined to form a 5- to 7-membered ring.

7. The reaction mixture according to claim 6 , wherein each R o and R o′ is independently substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl moiety, an amine, a substituted or unsubstituted aryl or a substituted or unsbustituted heteroaryl moiety.

8. The reaction mixture according to claim 1 , wherein said liganded metal atom is Ir or Rh.

9. The reaction mixture according to claim 1 , wherein said liganded metal atom is formed in situ by complexing the metal atom with the ligand, wherein said metal atom is provided by a source of a metal atom.

10. The reaction mixture according to claim 9 , wherein said metal atom source is [M(alkene) 2 X], wherein M is the metal atom, X is halide or alkoxy moieties.

11. The reaction mixture according to claim 1 , wherein said catalyst is bound to a solid support.

12. The reaction mixture according to claim 1 , wherein said reaction mixture further comprises the silylated analogue of said arene substrate.

13. The reaction mixture according to claim 12 , wherein the silylated analogue is further functionalized with BR 7 R 8 .

14. The reaction mixture according to claim 1 , wherein said silicon source is a silane having at least one heteroatom and is in a molar ratio with said arene substrate of less than 10:1.

15. The reaction mixture according to claim 1 , wherein said silicon source is a hydrosilane having at least one heteroatom and is in a molar ratio with said substrate of less than 10:1.

16. The reaction mixture according to claim 1 , wherein said silicon source is a silane having at least one heteroatom and is in a molar ratio with said substrate of less than 10:1.

17. The reaction mixture according to claim 1 , wherein said silicon source is a hydrosilane having at least one heteroatom and is in a molar ratio with said substrate of less than 10:1, and said metal atom is Ir or Rh.

18. The reaction mixture according to claim 1 , wherein said silicon source is a silane having at least one heteroatom and is in a molar ratio with said substrate of less than 10:1, and said substrate is not substituted with a directing group.

19. The reaction mixture according to claim 1 , further comprising an organic solvent.

20. The reaction mixture of claim 1 , wherein in said liganded metal ligand is a substituted or unsubstituted phenanthroline, a substituted or unsubstituted bipyridine and a combination thereof.

21. A method for forming a silyl arene compound, said method comprising:
(a) forming a reaction mixture according to claim 1 ; and
(b) incubating said reaction mixture under conditions appropriate to form said silylarene compound.

22. The method according to claim 21 , wherein said silyl arene compound is functionalized with the silyl moiety at the sterically least hindered site of the arene substrate.

23. The method according to claim 21 , further comprising isolating the silyl arene compound.

24. The method according to claim 21 , wherein said silyl arene is further functionalized with BR 7 R 8 .

25. The method according to claim 21 , wherein said silyl arene is submitted to a reaction in which said silyl moiety is subsituted by another moiety.

26. The method according to claim 23 , wherein the silyl moiety, BR 7 R 8 and a combination thereof is substituted by another moiety.

27. The method according to claim 21 , wherein said reaction mixture is incubat

Assignees

• Univ California

Inventors

• Hartwig John F
• Cheng Chen
• Wilson Tyler

Classifications

• C07F7/0854

  Chemistry & Metallurgy · mapped topic

• C07F7/0881

  Chemistry & Metallurgy · mapped topic

• C07F7/188

  by reactions involving the formation of Si-O linkages · CPC title

• C07F7/0807 Primary

  comprising Si as a ring atom · CPC title

• C07F7/085

  Chemistry & Metallurgy · mapped topic