84500-82-3Relevant academic research and scientific papers
Cine-Silylative Ring-Opening of α-Methyl Azacycles Enabled by the Silylium-Induced C-N Bond Cleavage
Zhang, Jianbo,Chang, Sukbok
supporting information, p. 12585 - 12590 (2020/08/21)
Described herein is the development of a borane-catalyzed cine-silylative ring-opening of α-methyl azacycles. This transformation involves four-step cascade processes: (i) exo-dehydrogenation of alicyclic amine, (ii) hydrosilylation of the resultant enamine, (iii) silylium-induced cis-β-amino elimination to open the ring skeleton, and (iv) hydrosilylation of the terminal olefin. The present borane catalysis also works efficiently for the C-N bond cleavage of acyclic tertiary amines. On the basis of experimental and computational studies, the silicon atom was elucidated to play a pivotal role in the β-amino elimination step.
Gold Catalyzed Photoredox C1-Alkynylation of N-Alkyl-1,2,3,4- tetrahydroisoquinolines by 1-Bromoalkynes with UVA LED Light
Zhao, Yichao,Jin, Jianwen,Chan, Philip Wai Hong
, p. 1313 - 1321 (2019/06/03)
A synthetic method that combines [Au2(m-dppm)2]Cl2 (dppm=bis(diphenylphosphanyl)methane) and UVA LED (LED=light emitting diode) light (365 nm) to catalyze the regioselective C1-alkynylation of N-alkyl-1,2,3,4-tetrahydroisoquinolines (THIQs) with alkynyl bromides is described. The reaction mechanism was delineated to involve a reductive quench pathway to generate the two posited radical species of the nitrogen-containing heterocycle and organic halide. In contrast, radical formation via an oxidative quench pathway was suggested to be operative in analogous control experiments with a 1-iodoalkyne. The usefulness of this carbon-carbon bond forming strategy was also exemplified by its application to the formal synthesis of the opioid analgesic drug methopholine and synthesis of a protoberberine alkaloid derivative.
Tropylium-Promoted Oxidative Functionalization of Tetrahydroisoquinolines
Oss, Giulia,De Vos, Sander D.,Luc, Kevin N. H.,Harper, Jason B.,Nguyen, Thanh V.
, p. 1000 - 1010 (2018/01/28)
Structural modification of the tetrahydroisoquinoline (THIQ) framework is of significant interest to organic chemists due to its central role in heterocyclic and medicinal chemistry. Here we demonstrate an efficient metal-free method for the oxidative fun
Aza-henry reactions of 3,4-dihydroisoquinoline
Ahamed, Muneer,Thirukkumaran, Thiru,Leung, Wing Yan,Jensen, Paul,Schroers, Jade,Todd, Matthew H.
, p. 5980 - 5988 (2011/02/22)
The aza-Henry reaction of 3,4-dihydroisoquinoline is reported. The reaction is favourable in excess nitromethane under ambient conditions. Isolation of the unstable reaction product is achieved by acylation or alkylation, allowing the synthesis of Reissert-like compounds in good yields from a one-pot, three-component coupling. The rates of reaction for dihydroisoquinoline and the corresponding benzylisoquinolinium ion have been investigated in the presence and absence of base. The reaction with dihydroisoquinoline probably proceeds via an azinic acid tautomer of nitromethane, a reaction pathway unavailable to the isoquinolinium ion. The traditionally problematic reduction of two of the resulting β-nitroamine derivatives was achieved, providing access to a number of new chiral vicinal diamines. 3,4-Dihydroisoquinoline reacts with nitromethane, likely via a cyclic mechanism employing nitromethane's azinic acid tautomer. The product may be alkylated or acylated. Alternatively a Reissert-like one-pot, three-component coupling may be used to generate a range of β-nitroamines which may be reduced to give new isoquinoline-derived chiral, vicinal diamines.
