US009381508B2 (12) United States Patent (10) Patent No.: US 9,381,508 B2 Shekhar et al. (45) Date of Patent: *Jul. 5, 2016 (54) PHOSPHINE LGANDS FOR CATALYTIC 3 1/2438 (2013.01); B01J 3 1/2466 (2013.01); REACTIONS B01J 31/2485 (2013.01); C07C I/30 (2013.01); (71) Applicant: AbbVie Inc., North Chicago, IL (US) C07C I/321 (2013.01); C07C 17/093 (2013.01); C07C4I/01 (2013.01); C07C 45/68 (72) Inventors: Shashank Shekhar, Vernon Hills, IL (2013.01); C07C 45/71 (2013.01); C07C (US); Thaddeus S. Franczyk, Lake 201/10 (2013.01); C07C 253/14 (2013.01); Villa, IL (US); David M. Barnes C07C 253/30 (2013.01); C07C 273/1854 res is . s (2013.01); C07C303/36 (2013.01); C07C Gurnee,Bristol, WIIL (US); AnthonyTravis B. R.Pun, Haight, 303/40 (2013.01); C07C319/14 (2013.01); Wadsworth, IL (US); Vincent S. Chan C07D 209/12 (2013.01); C07D 209/34 Evanston. It (US) s s (2013.01); C07D 209/42 (2013.01); C07D VanSlon, 213/76 (2013.01); C07D 239/54 (2013.01); C07D 265/30 (2013.01); C07D 295/033 (73) Assignee: ABBVIE INC., North Chicago, IL (US) (2013.01); C07F I/02 (2013.01); C07F 5/025 (*)c Notice:- r Subject to any site- the still (2013.01);9/509 (2013.01); C07F 9/4021C07F 9/5072 (2013.01); (2013.01); C07F patent 1s extended or adjusted under C07F 9/65683 (2013.01); B01.J. 3 1/189 U.S.C. 154(b) by 0 days. (2013.01); B01.J 2231/4211 (2013.01); B01.J This patent is Subject to a terminal dis- 2231/4227 (2013.01); B01J 2231/4277 claimer. (2013.01); B01.J 2231/4283 (2013.01); B01.J 2231/4288 (2013.01); B01J 2231/4294 (21) Appl. No.: 14/834,420 (2013.01); B01J 2231/44 (2013.01); B01.J 2531/0205 (2013.01); B01J 2531/0266 (22) Filed: Aug. 24, 2015 (2013.01); B01J 2531/0288 (2013.01); B01.J. 2531/824 (2013.01); B01.J 2540/10 (2013.01); (65) Prior Publication Data B01J 2540/40 (2013.01); C07C 2531/24 (2013.01); C07C 2531/26 (2013.01); Y02P US 2015/O36O215A1 Dec. 17, 2015 20/52 (2015.11) Related U.S. Application Data (58) Field of Classification Search CPC ...... C07F 9/4021; C07F 9/509; C07F 9/5072; (63) Continuation of application No. 14/611,943, filed O CO7F 9/65683 Feb. 2, 2015, now Pat. No. 9,200,021, which is a See application file for complete search history. Aug.continuation 21, 2012, of applicationnow Pat No. No. 8,975.443, 13/591,117, which filed is on a ()56 Refeeees Citede continuation-in-part of application No. 13/184.425, U.S. PATENT DOCUMENTS filed on Jul. 15, 2011, now Pat. No. 8,841,487. 4,239,888 A 12, 1980 M11 (60) Eypal application No. 61/365.293, filed on Jul. 4,588,729 A 5, 1986 Nishi et al. s (Continued) (51) Int. Cl. BOI 3/18 (2006.01) FOREIGN PATENT DOCUMENTS BOI.3L/24 (2006.01) DE 1992.0847 A1 11, 2000 CD7C I/30 (2006.01) EP O647648 A1 4, 1995 C07C I/32 (2006.01) (Continued) C07C 17/093 (2006.01) CD7C 20/0 (2006.01) OTHER PUBLICATIONS CD7C 25.3/4 (2006.01) Rosen et al., “Mild Pd-Catalyzed N-Arylation of C07C 253/30 (2006.01) Methanesulfonamide and Related Nucleophiles: Avoiding Poten C07C 273/18 (2006.01) tially Genotoxic Reagents and Byproducts.” Org. Lett. 13(10):2564 C07C303/36 (2006.01) 2567 (2011). C07C303/240 (2006.01) Continued C07C39/4 (2006.01) (Continued) CD7C4I/OI (2006.01) Primary Examiner — Joseph Kosack CD7C 45/68 (2006.01) C07C 45/71 (2006.01) (74) Attorney, Agent, or Firm — Neal, Gerber & Eisenberg C07D 209/12 (2006.01) LLP CO7D 209/34 (2006.01) CO7D 209/242 (2006.01) C07D 213/76 (2006.01) (57) ABSTRACT Continued Thee d1SCIOSurediscl 1S directedd1rected to:to: (a) phosphacyclephospinacycle ligands;11gands; (b) (Continued) catalyst compositions comprising phosphacycle ligands; and c) methods of using Such phosphacycle ligands and catalyst (52) CPCU.S. Cl............. Bo1.J 31/249 (2013.01); B01J 31/2419 compositions in bond forming reactions. (2013.01); B01J 3 1/2423 (2013.01); B01.J 22 Claims, No Drawings US 9,381.508 B2 Page 2 (51) Int. Cl. 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