IP Library Granted Patent US 9,150,516
Granted Patent B2
US 9,150,516 · App. 13/444,676 · Granted Oct 6, 2015

Fluorination of organic compounds

Inventors: Tobias Ritter (Cambridge, MA); Pingping Tang (Quincy, MA)
Assignee: President and Fellows of Harvard College
C07D233/28C07B39/00C07C17/16C07C41/22C07C45/63C07C67/307C07C201/12C07C209/74C07D233/10C07J1/0059C07B2200/05
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Quick Facts
Patent No.
US 9,150,516
App. No.
13/444,676
Granted
Oct 6, 2015
Kind
B2
Abstract

Methods for fluorinating organic compounds are described herein.

Claims (29)

1. A compound of formula (I):

wherein

R 1 and R 2 are each independently selected from C 6-12 aryl, C 6-12 aralkyl, 6-12 membered heteroaryl, 6-12 membered heteroaralkyl, 6-12 membered heterocyclyl and 6-12 membered heterocyclylalkyl, each of which is substituted with 0-3 occurrences of R 5 ;

X is an optionally substituted C 2 -C 5 alkenylene moiety

each R 5 is independently selected from halo, C 1-8 alkyl, C 1-8 haloalkyl, C 1-8 alkoxy, C 6-12 aryl and 6-12 membered heteroaryl.

2. The compound of claim 1 , wherein R 1 and R 2 are each independently selected from C 6-12 aryl, 6-12 membered heteroaryl and 6-12 membered heterocyclyl.

3. The compound of claim 1 , wherein X is an optionally substituted C 2 alkenylene.

4. The compound of claim 1 , wherein the compound of formula (I) is a compound of formula (Ia):

wherein

each R 3 is independently selected from C 1-8 alkyl, nitro, cyano, halo, C 1-8 haloalkyl, C 1-8 alkoxy, C 6-12 aryl, C 6-12 aralkyl, 6-12 membered heteroaryl, 6-12 membered heterocyclyl and 6-12 membered heterocyclylalkyl; and

n is 0, 1 or 2.

5. The compound of claim 1 , wherein the compound of formula (I) is a compound of formula (Ib):

6. The compound of claim 1 , wherein each R 5 is independently selected from C 1-8 alkyl, C 1-8 haloalkyl and C 1-8 alkoxy.

7. The compound of claim 1 , wherein the compound of formula (I) is a compound of formula (Ic):

8. A method of producing a compound of claim 1 , the method comprising reacting a compound of formula (II):

wherein R 1 , R 2 and X are as defined in claim 1 ; wherein

LG is a leaving group; and

Q is an anion;

with a fluorine source to produce the compound of formula (I).

9. The method of claim 8 , wherein R 1 and R 2 are each independently selected from C 6-12 aryl, 6-12 membered heteroaryl and 6-12 membered heterocyclyl.

10. The method of claim 8 , wherein X is an optionally substituted C 2 alkenylene.

11. The method of claim 8 , wherein each R 5 is independently selected from C 1-8 alkyl, C 1-8 haloalkyl and C 1-8 alkoxy.

12. The method of claim 8 , wherein the fluorine source is F − or a salt thereof.

13. A reaction mixture comprising a compound of claim 1 , an organic compound and a fluorine source.

14. A composition comprising a compound of formula (I) and an additional component

wherein

R 1 and R 2 are each independently selected from C 6-12 aryl, C 6-12 aralkyl, 6-12 membered heteroaryl, 6-12 membered heteroaralkyl, 6-12 membered heterocyclyl and 6-12 membered heterocyclylalkyl, each of which is substituted with 0-3 occurrences of R 5 ;

each R 5 is independently selected from halo, C 1-8 alkyl, C 1-8 haloalkyl, C 1-8 alkoxy, C 6-12 aryl and 6-12 membered heteroaryl;

X is an optionally substituted C 2 -C 5 alkenylene moiety.

Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 10, 2014
From: RITTER, TOBIAS; TANG, PINGPING
To: PRESIDENT AND FELLOWS OF HARVARD COLLEGE
Reel/Frame 031937/0338 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 10, 2013
From: RITTER, TOBIAS; TANG, PINGPING
To: PRESIDENT AND FELLOWS OF HARVARD COLLEGE
Reel/Frame 031573/0248 →
CONFIRMATORY LICENSE Recorded Oct 2, 2012
From: HARVARD UNIVERSITY
To: NATIONAL INSTITUTES OF HEALTH (NIH), U.S. DEPT. OF HEALTH AND HUMAN SERVICES (DHHS), U.S. GOVERNMENT
Reel/Frame 029065/0810 →
Continuity (2)
Provisional Application 61474535 · Apr 12, 2011
Related Publication 20120316341A1 · Dec 13, 2012