Silylated derivatives of aromatic heterocycles

Patent metadata

Field	Value
Publication number	US-10919917-B2
Application number	US-201916705408-A
Country	US
Kind code	B2
Filing date	Dec 6, 2019
Priority date	Aug 6, 2014
Publication date	Feb 16, 2021
Grant date	Feb 16, 2021

Abstract

The present disclosure describes methods for silylating heteroaromatic derivatives, comprising the use of hydrosilanes and potassium hydroxide.

First claim

What is claimed:

1. A method of preparing silylated compound comprising a moiety of Formula (I) or Formula (II):

the method comprising:
contacting a substrate containing a

moiety with a hydrosilane of formula (R 1 ) 3−m Si(H) m+1 and potassium hydroxide (KOH), under conditions to form the silylated compound, the method resulting in the formation of the silylated compound comprising the moiety of Formula (I) or Formula (II);
wherein
m is 0, 1, or 2;
R 1 is independently optionally substituted C 1-12 alkyl, C 1-12 heteroalkyl, or an optionally substituted 5- or 6-membered aryl or heteroaryl, and, if substituted, the substituents are independently alkyl, alkenyl, aryl, heteroaryl, hydroxyl, C 1 -C 20 alkoxy, C 5 -C 20 aryloxy, C 2 -C 20 alkoxycarbonyl, C 5 -C 20 aryloxycarbonyl, amino, optionally protected carboxyl, carboxylato, cyano, halo, phosphonato, phosphoryl, phosphanyl, phosphino, sulfonato, C 1 -C 20 alkylsulfanyl, C 5 -C 20 arylsulfanyl, C 1 -C 20 alkylsulfonyl, C 5 -C 20 arylsulfonyl, C 1 -C 20 alkylsulfinyl, C 5 -C 20 arylsulfinyl, sulfonamido, amido, imino, nitro, nitroso, mercapto, optionally protected formyl, C 1 -C 20 thioester, cyanato, thiocyanato, isocyanate, thioisocyanate, carbamoyl, epoxy, styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronato, or boryl;
X is NR 2 , O, or S;
R 2 is an amine protecting group, an optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkaryl or optionally substituted alk-heteroaryl;

is a heteroaromatic moiety containing y additional nitrogens in the ring structure, where y=0 or 1 when X is O or S, or y=0, 1, or 2 when X is NR2; and

is an aromatic moiety containing x nitrogen atoms in the ring structure, where x=0, 1, or 2.

2. The method of claim 1 , resulting in the formation of the silylated compound comprising the moiety of Formula (I) having a structure of:

3. The method of claim 1 , resulting in the formation of the silylated compound comprising the moiety of Formula (I) having a structure of:

4. The method of claim 1 , resulting in the formation of the silylated compound comprising the moiety of Formula (I) having a structure of:

5. The method of claim 1 , resulting in the formation of the silylated compound comprising the moiety of Formula (II) having a structure of:

6. The method of claim 1 , resulting in the formation of the silylated compound comprising the moiety of Formula (II) having a structure of:

7. The method of claim 1 , resulting in the formation of the silylated compound comprising the moiety of Formula (II) having a structure of:

8. The method of claim 1 , wherein m=0.

9. The method of claim 1 , wherein m=1, optionally wherein R 1 is independently tert-butyl, —C(CH 3 ) 2 (CN), pyridine, or an alkyl substituted heterocycloalkyl.

10. The method of claim 2 , wherein m=1, optionally wherein R 1 is independently tert-butyl, —C(CH 3 ) 2 (CN), pyridine, or an alkyl substituted heterocycloalkyl.

11. The method of claim 5 , wherein m=1, optionally wherein R 1 is independently tert-butyl, —C(CH 3 ) 2 (CN), pyridine, or an alkyl substituted heterocycloalkyl.

12. The method of claim 1 , wherein m=2.

13. The method of claim 1 , wherein R 1 is independently optionally substituted C 1-12 alkyl, optionally substituted heteroaryl or optionally substituted C 2-12 heterocycloalkyl.

14. The method of claim 2 , wherein R 1 is independently optionally substituted C 1-12 alkyl, optionally substituted heteroaryl or optionally substituted C 2-12 heterocycloalkyl.

15. The method of claim 5 , wherein R 1 is independently optionally substituted C 1-12 alkyl, optionally substituted heteroaryl or optionally substituted C 2-12 heterocycloalkyl.

16. The method of claim 1 where R 1 is independently optionally substituted cyclic alkyl or branched alkyl or cyclic or branched heteroalkyl.

17. The method of claim 2 , wherein R 1 is independently optionally substituted cyclic alkyl or branched alkyl or cyclic or branched heteroalkyl.

18. The method of claim 5 , wherein R 1 is independently optionally substituted cyclic alkyl or branched alkyl or cyclic or branched heteroalkyl.

19. The method of claim 9 , wherein R 1 is independently tert-butyl, —C(CH 3 ) 2 (CN), pyridine, or an alkyl substituted heterocycloalkyl.

20. The method of claim 10 , wherein R 1 is independently tert-butyl, —C(CH 3 ) 2 (CN), pyridine, or an alkyl substituted heterocycloalkyl.

21. The method of claim 11 , wherein R 1 is independently tert-butyl, —C(CH 3 ) 2 (CN), pyridine, or an alkyl substituted heterocycloalkyl.

22. The method of claim 1 , wherein X is NR 2 .

23. The method of claim 1 , wherein X is O.

24. The method of claim 1 , wherein X is S.

25. The method of claim 1 , resulting in the formation of the silylated compound comprising the moiety of Formula (I) having a structure of:

or of the silylated compound comprising the moiety of Formula (II) having a structure of:

where R′ is halo, C 1 -C 24 alkoxy, C 2 -C 24 alkenyloxy, C 2 -C 24 alkynyloxy, C 5 -C 24 aryloxy, C 6 -C 24 aralkyloxy, C 6 -C 24 alkaryloxy, C 1 -C 24 alkylcarbonyl (—CO-alkyl), C 6 -C 24 arylcarbonyl (—CO-aryl)), C 2 -C 24 alkylcarbonyloxy (—O—CO-alkyl), C 6 -C 24 arylcarbonyloxy (—O—CO-aryl)), C 2 -C 24 alkoxycarbonyl ((CO)—O-alkyl), C 6 -C 24 aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)—X where X is halo), C 2 -C 24 alkylcarbonato (—O—(CO)—O-alkyl), C 6 -C 24 arylcarbonato (—O—(CO)—O-aryl), carboxy (—COOH), carboxylato (—COO—), carbamoyl (—(CO)—NH 2 ), mono-(C 1 -C 24 alkyl)-substituted carbamoyl (—(CO)NH(C 1 -C 24 alkyl)), di-(C 1 -C 24 alkyl)-substituted carbamoyl (—(CO)—N(C 1 -C 24 alkyl) 2 ), mono-(C 1 -C 24 haloalkyl)-substituted carbamoyl (—(CO)—NH(C 1 -C 24 alkyl)), di-(C 1 -C 24 haloalkyl)-substituted carbamoyl (—(CO)—N(C 1 -C 24 alkyl) 2 ), mono-(C 5 -C 24 aryl)-substituted carbamoyl (—(CO)—NH-aryl), di-(C 5 -C 24 aryl)substituted carbamoyl (—(CO)—N(C 5 -C 24 aryl) 2 ), di-N—(C 1 -C 24 alkyl), N—(C 5 -C 24 aryl)-substituted carbamoyl, thiocarbamoyl (—(CS)—NH 2 ), mono-(C1-C24 alkyl)-substituted thiocarbamoyl (—(CO)—NH(C 1 -C 24 alkyl))

Assignees

• California Inst Of Techn

Inventors

• Toutov Anton
• Betz Kerry
• Fedorov Alexey
• Stoltz Brian M
• Liu Wenbo
• Grubbs Robert H

Classifications

• C07F7/0801 Primary

  General processes · CPC title

• C07F7/0827

  Syntheses with formation of a Si-C bond · CPC title

• C07F7/0832

  Other preparations · CPC title

• C07D209/12

  Radicals substituted by oxygen atoms · CPC title