Journal ArticleDOI
Mechanistic Studies on the Catalytic Asymmetric Mannich-Type Reaction with Dihydroisoquinolines and Development of Oxidative Mannich-Type Reactions Starting from Tetrahydroisoquinolines
Christian Dubs,Yoshitaka Hamashima,Naoki Sasamoto,Thomas M. Seidel,Shoko Suzuki,Daisuke Hashizume,Mikiko Sodeoka +6 more
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TLDR
Detailed mechanistic studies on recently reported asymmetric addition reactions of malonates to dihydroisoquinolines (DHIQs) catalyzed by chiral Pd(II) complexes were carried out, allowing the efficient synthesis of optically active tetrahydrobenzo[a]quinolizidine derivatives via intramolecular Michael reaction.Abstract:
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 was generated in situ by the reaction of DHIQ with (Boc)2O, and cooperative action of the Pd(II) complex as an acid−base catalyst allowed the formation of a chiral Pd enolate and a reactive iminium ion via α-fragmentation. The iminium ion was also accessible via oxidation with DDQ as an oxidant, and a catalytic asymmetric oxidative Mannich-type reaction was achieved with tetrahydroisoquinolines (THIQs) as starting materials. This oxidation protocol was applicable to N-acryloyl-protected THIQs, allowing the efficient synthesis of optically active tetrahydrobenzo[a]quinolizidine derivatives via intramolecular Michael reaction.read more
Citations
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Journal ArticleDOI
The Cross-Dehydrogenative Coupling of C sp 3H Bonds: A Versatile Strategy for CC Bond Formations
TL;DR: This Review highlights the recent progress in the field of cross-dehydrogenative C sp 3C formations and provides a comprehensive overview on existing procedures and employed methodologies.
Journal ArticleDOI
Catalytic Enantioselective Formation of C−C Bonds by Addition to Imines and Hydrazones: A Ten-Year Update
Journal ArticleDOI
Recent development of direct asymmetric functionalization of inert C–H bonds
Chao Zheng,Shu-Li You +1 more
TL;DR: The area of direct asymmetric functionalization of inert C-H bonds has attracted considerable attention in recent years as discussed by the authors, and a lot of strategies have emerged including asymmetric C−H bond insertion by metal carbenoids or analogs, cross dehydrogenative coupling, [1,5]-hydride transfer, C-h bond functionalization involving a transient metal-carbon species and other miscellaneous methods.
Journal ArticleDOI
Direct α-functionalization of saturated cyclic amines.
TL;DR: Methods for the direct α-functionalization of saturated cyclic amines are described and transition-metal-catalyzed reactions involving other intermediates have been treated as a separate and fourth class.
Journal ArticleDOI
Dehydrierende Kreuzkupplungen von C sp 3‐H‐Bindungen: vielseitige Verfahren zur Bildung von C‐C‐Bindungen
TL;DR: Li et al. as discussed by the authors proposed a cross-dehydrogenative coupling (CDC) strategy, in which the reaktiven Zwischenstufen durch Aktivierung der beiden C-H-Bindungen in situ gebildet werden.
References
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Journal ArticleDOI
Modern Variants of the Mannich Reaction
TL;DR: Modern variants of the Mannich reaction that expand the potential of the classical intermolecular reaction significantly and enable efficient control of the regioselectivities and stereoselectivity are therefore the topic of intensive research.
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Chemistry and biology of the tetrahydroisoquinoline antitumor antibiotics.
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Additions of Organometallic Reagents to C=N Bonds: Reactivity and Selectivity
Journal ArticleDOI
Asymmetric Transfer Hydrogenation of Imines
Journal ArticleDOI
The direct catalytic asymmetric mannich reaction.
TL;DR: The direct catalytic asymmetric addition of unmodified carbonyl compounds to preformed or in situ-generated imines has emerged as a promising new route to optically enriched alpha- and beta-amino acid derivatives, beta-lactams, and 1,2- and gamma-aminos alcohols.
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