IP Library Granted Patent US 9,856,275
Granted Patent B2
US 9,856,275 · App. 14/767,103 · Granted Jan 2, 2018

Synthesis and use of fluorinated compounds

Inventors: Gary Alan Molander (Broomall, PA); Oana Andreea Argintaru (Philadelphia, PA)
Assignee: The Trustees of the University of Pennsylvania
C07F5/04C07B39/00C07C17/263C07C22/08C07C29/36C07C41/22C07C41/26C07C41/30C07C67/343C07D209/08C07F5/02C07B2200/09
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Quick Facts
Patent No.
US 9,856,275
App. No.
14/767,103
Granted
Jan 2, 2018
Kind
B2
Abstract

The invention is directed to the preparation of fluorinated compounds and their use in organic synthesis. In particular, the invention is directed to methods of reacting compounds of structure with R f —CH═N 2 or (CF 3 ) 2 C═N 2 to form a perfluoroalkylate or -arylated compounds, and products derived from these reactions, where X, Y B , and R f are described herein.

Claims (23)

1. A compound of Formula Ia:

wherein

n is an integer from 1 to 50;

X is optionally substituted C 2-20 alkyl; optionally substituted C 1-20 heteroalkyl; optionally substituted C 2-20 alkenyl; optionally substituted C 2-20 alkynyl; optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, or fluorine; and

Y is —B-pinacol; —B(OR) 2 ; —BF 3 K; or BZ 2 ;

wherein each R is independently H or C 1-6 alkyl; and Z is halogen.

2. The compound of claim 1 , wherein n is 1 to 5.

3. The compound of claim 1 , wherein n is 6 to 10.

4. The compound of claim 1 , wherein n is 11 to 50.

5. The compound of claim 1 , wherein n is 1 or 2.

6. The compound of claim 1 , wherein n is 1.

7. The compound of claim 1 , wherein X is optionally substituted aryl.

8. The compound of claim 7 , wherein the aryl is optionally substituted phenyl, naphthyl, or fluorenyl.

9. The compound of claim 7 , wherein the aryl is substituted with 1, 2, or 3 substitutents independently selected from the group consisting of C 1-6 alkyl; C 1-6 alkenyl; C 1-6 alkynyl, —OC 1-6 alkyl; —OC 1-6 alkenyl; —C(O)C 1-6 alkyl; —C(O)-aryl; —C(O)-heteroaryl; —C(O)OC 1-6 alkyl; —C(O)O-aryl; —C(O)O-heteroaryl; —OC(O)C 1-6 alkyl; —OC(O)-aryl; —OC(O)-heteroaryl; aryl; heteroaryl; halogen; haloalkyl; nitro, —OH, —CN; or —SO 2 N(R 1 ) 2 , wherein each R 1 is independently H or —C 1-6 alkyl.

10. The compound of claim 1 , wherein X is:

11. The compound of claim 1 , wherein X is optionally substituted heteroaryl.

12. The compound of claim 11 , wherein the heteroaryl is furanyl, imidazolyl, pyrrolidinyl, pyrimidinyl, tetrazolyl, thienyl, pyridyl, pyrrolyl, N-methylpyrrolyl, quinolinyl, or isoquinolinyl.

13. The compound of claim 11 , wherein the heteroaryl is substituted with 1, 2, or 3 substitutents independently selected from the group consisting of C 1-6 alkyl; —C 1-6 alkenyl; —OC 1-6 alkyl; —OC 1-6 alkenyl; —C(O)C 1-6 alkyl; —C(O)-aryl; —C(O)-heteroaryl; —C(O)OC 1-6 alkyl; —C(O)O-aryl; —C(O)O-heteroaryl; —OC(O)C 1-6 alkyl; —OC(O)-aryl; —OC(O)-heteroaryl; aryl; heteroaryl; halogen; haloalkyl; nitro, —OH; —CN; or —SO 2 N(R 1 ) 2 , wherein each R 1 is independently H or —C 1-6 alkyl.

14. The compound of claim 11 , wherein X is:

15. The compound of claim 1 , wherein n is 1 or 2.

16. The compound of claim 1 , wherein n is 3 to 50.

17. The compound of claim 1 that is selected from the group consisting of:

18. The compound of claim 1 that is an isolated compound.

Assignments (3)
CONFIRMATORY LICENSE Recorded Jun 15, 2016
From: UNIVERSITY OF PENNSYLVANIA
To: NATIONAL INSTITUTES OF HEALTH (NIH), U.S. DEPT. OF HEALTH AND HUMAN SERVICES (DHHS), U.S. GOVERNMENT
Reel/Frame 039027/0148 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 11, 2015
From: MOLANDER, GARY ALAN; ARGINTARU, OANA ANDREEA
To: THE TRUSTEES OF THE UNIVERSITY OF PENNSYLVANIA
Reel/Frame 036298/0421 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 11, 2015
From: MOLANDER, GARY A.; ARGINTARU, OANA ANDREEA
To: THE TRUSTEES OF THE UNIVERSITY OF PENNSYLVANIA
Reel/Frame 036298/0486 →
Continuity (3)
Provisional Application 61763595 · Feb 12, 2013
Provisional Application 61897371 · Oct 30, 2013
Related Publication 20160002270A1 · Jan 7, 2016