Intermolecular c-h silylation of unactivated arenes

Patent metadata

Field	Value
Publication number	US-2016200639-A1
Application number	US-201414916787-A
Country	US
Kind code	A1
Filing date	Sep 8, 2014
Priority date	Sep 6, 2013
Publication date	Jul 14, 2016
Grant date	—

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, in a ratio less than 10:1 to the substrate, wherein, when the silylatable moiety is a five-membered heteroarene ring containing an intrannular heteroatom selected from N, S and O, the silicon source includes at least one group bound to Si which is other than an alkyl group or a hydrogen, e.g., the silicon source is not HSiR 3 , in which R is alkyl.

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 members selected from 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, —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 a member selected from substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl
wherein
R 7 and R 8 are members independently selected from 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 a member selected from substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl.

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

4 . The reaction mixture according to any preceding claim, wherein said ligand is a phosphorus-containing ligand.

5 . The reaction mixture according to any preceding claim, wherein said ligand is a phosphorus-containing ligand, which is a biaryl ligand.

6 . The reaction mixture according to any preceding claim, wherein said ligand is a phosphorus-containing ligand, which is a biaryl ligand having the formula:

wherein
R a , R b , R c , R d , R e , R a′ , R b′ , R c′ , R d′ , and R o′ , are each members independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, halogen, CN, CF 3 , acyl, —SO 2 NR e R f , —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 a member selected from substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl;
R e and R f include members independently selected from 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 selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl moiety, an amine, a substituted or unsubstituted aryl or a substituted or unsubstituted heteroaryl moiety.

8 . The reaction mixture according to any preceding claim, wherein said liganded metal atom is selected from Ir and Rh.

9 . The reaction mixture according to any preceding claim, 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 selected from halide and alkoxy moieties, and an exemplary alkene is a cycloalkene, e.g., cyclooctadiene (COD).

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

12 . The reaction mixture according to any preceding claim, 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 any preceding claim, 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 any preceding claim, 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 any preceding claim, 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 any preceding claim, 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 selected from Ir and Rh.

18 . The reaction mixture according to any preceding claim, 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 any preceding claim, further comprising an organic solvent.

20 . The reaction mixture of any of claims 1 - 3 and 8 - 19 , wherein said ligand is a member selected from 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 any preceding claim; and (b) incubating said reaction mixture under conditions appropriate to form said silylarene compound.

22 . The method according to claim 19 , 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 19 , further comprising isolating the silyl arene compound.

24 . The method according to claim 19 , wherein said silyl arene is further functionalized with BR 7 R 8 .

25 . The method a

Assignees

• Univ California

Inventors

• Hartwig John F
• Cheng Chen
• Wilson Tyler

Classifications

• C07F7/188

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

• C07F7/0829

  Hydrosilylation reactions · CPC title

• C07F7/1804

  Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896) · CPC title

• C07F7/1876

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

• C07F7/0807 Primary

  comprising Si as a ring atom · CPC title