Review Recent Developments in Pd-catalyzed Carbonylation Reaction Li Yuanhe Supervisors: Prof. Yang Prof. Chen Prof. Tang
History 1962, E. Fischer Z. Nafurforsch. 1962, 17b, 484. 1963, R. Heck J. Org. Chem. 1972, 37(14), 2320. 1972, Heck reaction 1974, R. Heck J. Org. Chem. 1974, 39(23), 3318. 2/39
Mechanism Migration or Insertion? Assume: No trans-insertion No stereo-wobbling 3/39
Mechanism Migration or Insertion? K. Noack And F. Calderazzo, J. Organometal. Chem. 1967, 10, 101. 4/39
Mechanism Migration or Insertion? B. Scott Williams, et. al., Organometallics 2009, 28, 1613 1615 Exception Gordon. K. Anderson, et. al., Acc. Chem. Res. 1984,17, 67-74 5/39
Mechanism Mostly dissociation-insertion (3/4-coordinate, not 4/5) Non-RDS fast process Kinetic study of >100 rxn of Ni, Pd, Pt. R.F. Heck, et. al., J. Am. Chem. Soc., 1976, 98, 4115. Exception Excessed or firm ligands C.H. Stam, et. al., Inorg. Chim. Acta, 1990, 169, 5. 6/39
Influencing factors CO substitution Electronic migrating R Nucleophilicity CO Pressure Sterically hindered P t Bu 3, BuPAd 2, bulky NHC Throw-away ligend (L) Py, MeCN > PR 3 > AcO -, Cl - R: n-alkyl anion > allylic, benzylic Ar: electron rich > electron poor Trans effect on R Trapping ligand Trans-effect / Pi-pushing effect Electronic CO δ + CO Ion effect: Li + > Na + Lewis acid Favor strong coordination ligand PMe 3 > PMe 2 Ph > PMePh 2 > CO Nucleophile / Bidentate ligand Binding angle Edward S. Petrov, et. al., React. Kinet. Catal. Lett., 1998, 64, 359. S. Sakaki, et.al., J. Am. Chem. Soc. 1983, 105, 2280. Kingsley J. Cavel, Coord. Chem. Rev. 1996, 155, 209. Tao Tu, et.al., Synthesis 2014, 46, 1689 1708. 7/39
Outline Equivalent intermediate C(sp) Pd C(sp 2 ) Pd C(sp 3 ) Pd Double Carbonylation C-H Activation - Carbonylation 8/39
Outline Equivalent intermediate C(sp) Pd C(sp 2 ) Pd C(sp 3 ) Pd Double Carbonylation C-H Activation - Carbonylation 9/39
C(sp) Pd Takahashi, T. et. al., Tetrahedron Lett. 1980, 21, 849. Takahashi, T. et. al., Tetrahedron Lett. 1980, 21, 849. Ishii, Y et. al.,. Tetrahedron Lett. 1999, 40, 1701. Ishii, Y et. al.,. Tetrahedron Lett. 1999, 40, 1701. 10/39
Outline Equivalent intermediate C(sp) Pd C(sp 2 ) Pd C(sp 3 ) Pd Double Carbonylation C-H Activation - Carbonylation 11/39
C(sp 2 ) Pd 12/39
C(sp 2 ) Pd Cowell, A.; Stille, J. K. J. Am. Chem. Soc. 1980, 102, 4193. 卿凤翎, et.al. J. Fluorine Chem. 2002, 114, 177. Hamel, N. et. al., Tetrahedron Lett. 1987, 28, 3237. Ban, Y. et. al., J. Chem. Soc., Chem. Commun. 1979, 698. Ban, Y. et. al., Tetrahedron 1985, 41, 375. 13/39
C(sp 2 ) Pd Chiusoli, G. P. et. al., J. Chem. Soc., Perkin Trans. 1 1997, 147. Norton, J. R. et. al., J. Am. Chem. Soc. 1981, 103, 7520. Dupont, J. et. al., Tetrahedron Lett. 2002, 43, 753. 赵世民, et. al., J. Org. Chem. 2005, 70, 2568. 14/39
C(sp 2 ) Pd Hirao, T. et. al., J. Org. Chem. 1997, 62, 8361. Gabriele, B. et. al.,; Adv. Synth. Catal. 2004, 346, 351. Gabriele, B. et. al., Synthesis 2007, 3083. 15/39
C(sp 2 ) Pd Larock, R. C. et. al., J. Org. Chem. 2004, 69, 6772. BILN 2061 Haddad, N.; Tan, J.; Farina, V. J. Org. Chem. 2006, 71, 5031. 16/39
Outline Equivalent intermediate C(sp) Pd C(sp 2 ) Pd C(sp 3 ) Pd Double Carbonylation C-H Activation - Carbonylation 17/39
C(sp 3 )-Pd Danishefsky, S. et. al.; Tetrahedron Lett. 1983, 24, 15. Yoshida, Z. et. al., J. Am. Chem. Soc. 1988, 110, 3994. Danishefsky, S et. al.; Tetrahedron Lett. 1983, 24, 15. Yoshida, Z. et. al., J. Am. Chem. Soc. 1988, 110, 3994. 18/39
C(sp 3 )-Pd Ilhyong Ryu, et. al., Acc. Chem. Res. 2014, 47, 1563 1574 19/39
Beyond small ring Cao, H.; Vieira, T. O. et. al.,; Alper, H. Org. Lett. 2011, 13, 11. Chouhan, G.; Alper, H. et. al., Org. Lett. 2010, 12, 192. Lenoble, G.; Urrutigoity, M.; Kalck, P. et. al., Tetrahedron Lett. 2001, 42, 3697 20/39
Outline Equivalent intermediate C(sp) Pd C(sp 2 ) Pd C(sp 3 ) Pd Double Carbonylation C-H Activation Carbonylation Outlook 21/39
Double Carbonylation Aklo Yamamoto, et. al., Tetrahedron Lett., 1982, 23, 3383 3386; J. Am. Chem. Soc., 1985, 107, 3235. M. Tanaka, et. al., J. Organomet. Chem., 1982, 233, C64 C66. (11 days later) 22/39
Double Carbonylation T. Watanabe, et. al., J. Org. Chem., 2001, 66, 5272 5274. 23/39
Double Carbonylation Yoshinori Kondo, et. al., Chem. Commun., 2006, 1739 1741 24/39
Double Carbonylation Takashi Takahashi, et. al., Tetrahedron, 2015, 71, 6354. 25/39
Outlook Equivalent intermediate C(sp) Pd C(sp 2 ) Pd C(sp 3 ) Pd Double Carbonylation C-H Activation Carbonylation Outlook 26/39
C-H Carbonylation Alkoxycarbonylation Aryl C(sp 2 )-H Booker-Milburn, K. I., Angew. Chem., Int. Ed. 2009, 48, 1830 1833. Shi, Z.-J. Dalton Trans. 2010, 39, 10442 10446. 27/39
C-H Carbonylation Lei, A.-W. Chem. Eur. J. 2011, 17, 9581 9585. 李福伟, et.al. Org. Lett. 2012, 14, 4130 4133. 28/39
C-H Carbonylation Yu, J.-Q. Chem. Sci. 2011, 2, 967 971. Shi, B.-F. Synlett. 2013, 24, 2274 2278 Shi, B.-F. Org. Biomol. Chem. 2014, 12, 2538 2542. Shih-Ching Chuang, Chem. Commun. 2013, 49, 11797 11799. 29/39
C-H Carbonylation Huang, H. ( 黄汉民 ) J. Am. Chem. Soc. 2012, 134, 9902 9905. Huang, H., et. al. Org. Lett., 2013, 15 (13), 3370 3373 30/39
C-H Carbonylation Inert C(sp3)-H carbonylation Fujiwara, Y., et. al. Chem. Lett. 1989, 1687. Fujiwara, Y., et. al. Chem. Lett. 1992, 1141 Fujiwara, Y., et. al. Organomet. Chem. 1994, 473, 329. Fujiwara, Y., et. al. Chem. Lett. 1991, 1433 Fujiwara, Y., et. al. Org. Lett. 1999, 557. 31/39
C-H Carbonylation Yu, J.-Q. J. Am. Chem. Soc. 2010, 132, 17378. Matthew J. Gaunt, Nature 2014, 510, 129 133 32/39
C-H Carbonylation Xi-Sheng Wang, Org. Lett. 2015, 17, 3698. 33/39
Outline Equivalent intermediate C(sp) Pd C(sp 2 ) Pd C(sp 3 ) Pd Double Carbonylation C-H Activation Carbonylation Outlook All carbon skeleton / ring system 34/39
All carbon skeleton Arcadi, A.; Cacchi, S.; Fabrizi, G.; Moro, L. Eur. J. Org. Chem. 1999, 1137. Arcadi, A.; Cacchi, S.; Del Rosario, M.; Fabrizi, G.; Marinelli, F. J. Org. Chem. 1996, 61, 9280. Y. Zhao, L. Jin, P. Li, A. Lei, J. Am. Chem. Soc. 2008, 130, 9429 9433. 35/39
All carbon skeleton Beller, M. Chem. Asian J. 2012, 7, 1199 1202. S.-C. Choi, Synth. Commun. 2001, 31, 1035 1039. Hiroaki Sasai, et. al., Synlett 2009, 2 310. R. F. W. Jackson, J. Chem. Soc. Perkin Trans. 1. 1997, 865 870. 36/39
All carbon ring system Wolfgang Oppolzer, et. al., Helvetica Chimica Acta, 1991, 74, 465 By Dr. You Lin, 2012 Jiahua Chen, and Zhen Yang, et. al., Org. Lett. 2005, 7, 1657. Jia-Hua Chen, Aiwen Lei, Zhen Yang, et..al., Synthesis, 2007, 16, 2565. Zhen Yang, and Yun-Dong Wu, et. al., J. Org. Chem. 2009, 74, 5049 37/39
All carbon ring system Other examples? Why rare? Chuangchuang Li, and Zhen Yang, Chem. Asian J. 2013, 8, 65. 38/39
Acknowledgements Prof. Yang, Prof. Chen, Prof. Tang Mr. You Lin B630 Everyone in Lab. and everyone here Ac 39/39
Supplement Lenoble, G.; Urrutigoity, M.; Kalck, P. Tetrahedron Lett. 2001, 42, 3697 Yu Bai, Dexter C. Davis, and Mingji Dai, Angew. Chem. Int. Ed. 2014, 53, 6519 6522 40/39
Regioselectivity of Allene Cyclocarbonylation Selective allylic substitution at more substituted site Ye, F.; Alper, H. J. Org. Chem. 2007, 72, 3218. Richard C. Larock* and John M. Zenner, J. Org. Chem. 1995, 60, 482-483 41/39
Sequence Selectivity Larock, R. C. J. Org. Chem. 2004, 69, 6772. Yang, Q.; Alper, H. J. Org. Chem. 2010, 75, 948. Xuefeng Jiang*, et. al., Angew. Chem. Int. Ed. 2015, 54, 14960 14964 42/39