Mechanistic Studies on the Catalytic Asymmetric Mannich-Type Reaction with Dihydroisoquinolines and Development of Oxidative Mannich-Type Reactions Starting from Tetrahydroisoquinolines
作者： Christian Dubs , Yoshitaka Hamashima , Naoki Sasamoto , Thomas M. Seidel , Shoko Suzuki
DOI: 10.1021/JO800800Y
关键词: Enantioselective synthesis 、 Intramolecular reaction 、 Chemistry 、 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone 、 Reaction mechanism 、 Mannich reaction 、 Iminium 、 Michael reaction 、 Addition reaction 、 Combinatorial chemistry 、 Organic chemistry
摘要: Detailed mechanistic studies on our recently reported asymmetric addition reactions of malonates to dihydroisoquinolines (DHIQs) catalyzed by chiral Pd(II) complexes were carried out. It was found that an N,O-acetal generated in situ the reaction DHIQ with (Boc)2O, and cooperative action complex as acid−base catalyst allowed formation a Pd enolate reactive iminium ion via α-fragmentation. The also accessible oxidation DDQ oxidant, catalytic oxidative Mannich-type achieved tetrahydroisoquinolines (THIQs) starting materials. This protocol applicable N-acryloyl-protected THIQs, allowing efficient synthesis optically active tetrahydrobenzo[a]quinolizidine derivatives intramolecular Michael reaction.
acs.org
core.ac.uk 
sci-hub.se 参考文章(99)
Zhiping Li, Chao-Jun Li, Highly Efficient Copper-Catalyzed Nitro-Mannich Type Reaction: Cross-Dehydrogenative-Coupling between sp3 C−H Bond and sp3 C−H Bond Journal of the American Chemical Society. ,vol. 127, pp. 3672- 3673 ,(2005) , 10.1021/JA050058J
Yoshihiro Matsumura, Yasuhisa Kanda, Kimihiro Shirai, Osamu Onomura, Toshihide Maki, A convenient method for synthesis of enantiomerically enriched methylphenidate from N-methoxycarbonylpiperidine. Organic Letters. ,vol. 1, pp. 175- 178 ,(1999) , 10.1021/OL9905046
S. Ruchirawat, M. Chaisupakitsin, N. Patranuwatana, J. L. Cashaw, V. E. Davis, A Convenient Synthesis of Simple Tetrahydroisoquinolines Synthetic Communications. ,vol. 14, pp. 1221- 1228 ,(1984) , 10.1080/00397918408076803
Tozo Fujii, Masashi Ohba, Chapter 3 – The Ipecac Alkaloids and Related Bases The Alkaloids: Chemistry and Biology. ,vol. 51, pp. 271- 321 ,(1998) , 10.1016/S0099-9598(08)60007-3
Eiko Ichikawa, Masato Suzuki, Kazuo Yabu, Matthias Albert, Motomu Kanai, Masakatsu Shibasaki, New entries in Lewis acid-Lewis base bifunctional asymmetric catalyst: catalytic enantioselective Reissert reaction of pyridine derivatives. Journal of the American Chemical Society. ,vol. 126, pp. 11808- 11809 ,(2004) , 10.1021/JA045966F
Yoshinori Yamamoto, Tomohisa Nakada, Hisao Nemoto, NMR detection of N-acyliminium ion intermediates generated from .alpha.-alkoxycarbamates Journal of the American Chemical Society. ,vol. 114, pp. 121- 125 ,(1992) , 10.1021/JA00027A017
Yasunori Tsuchiya, Yoshitaka Hamashima, Mikiko Sodeoka, A new entry to Pd-H chemistry: catalytic asymmetric conjugate reduction of enones with EtOH and a highly enantioselective synthesis of warfarin. Organic Letters. ,vol. 8, pp. 4851- 4854 ,(2006) , 10.1021/OL0619157
Shun-Ichi Murahashi, Yasushi Imada, Toru Kawakami, Kazuhito Harada, Yoshiharu Yonemushi, Naomi Tomita, Enantioselective Addition of Ketene Silyl Acetals to Nitrones Catalyzed by Chiral Titanium Complexes. Synthesis of Optically Active β-Amino Acids Journal of the American Chemical Society. ,vol. 124, pp. 2888- 2889 ,(2002) , 10.1021/JA0176649
Shinji Yamada, Chisako Morita, Face-selective addition to a cation-π complex of a pyridinium salt: Synthesis of chiral 1,4-dihydropyridines Journal of the American Chemical Society. ,vol. 124, pp. 8184- 8185 ,(2002) , 10.1021/JA0203317
Osamu Onomura, Yasuhisa Kanda, Yasuharu Nakamura, Toshihide Maki, Yoshihiro Matsumura, Copper ion-catalyzed asymmetric carbon–carbon bond-forming reaction at the 2-position of a piperidine skeleton Tetrahedron Letters. ,vol. 43, pp. 3229- 3231 ,(2002) , 10.1016/S0040-4039(02)00449-5