2809-78-1Relevant articles and documents
Halogen-Substituted Allenyl Ketones through Ring Opening of Nonstrained Cycloalkanols
Wu, Penglin,Ma, Shengming
supporting information, p. 2533 - 2537 (2021/04/13)
An efficient synthesis of halogen-substituted allenyl ketones via Ag-catalyzed oxidative ring opening of allenyl cyclic alcohols under mild reaction conditions has been achieved. The reaction features a wide substrate scope and excellent regioselectivity. The synthetic potential of the products has been demonstrated by their conversion to stereodefined alkenes and heterocyclic compounds.
Enantio- And Diastereodivergent Construction of 1,3-Nonadjacent Stereocenters Bearing Axial and Central Chirality through Synergistic Pd/Cu Catalysis
Zhang, Jiacheng,Huo, Xiaohong,Xiao, Junzhe,Zhao, Ling,Ma, Shengming,Zhang, Wanbin
supporting information, p. 12622 - 12632 (2021/08/31)
In contrast to the widely explored methods for the asymmetric synthesis of molecules bearing a single stereocenter or adjacent stereocenters, the concurrent construction of 1,3-stereogenic centers in an enantio- and diastereoselective manner remains a challenge, especially in acyclic systems. Herein, we report an enantio- and diastereodivergent construction of 1,3-nonadjacent stereocenters bearing allenyl axial and central chirality through synergistic Pd/Cu-catalyzed dynamic kinetic asymmetric allenylation with racemic allenylic esters. The protocol is suitable for a wide range of substrates including the challenging allenylic esters with less sterically bulky substituents and provided chiral allenylic products bearing 1,3-nonadjacent stereocenters with high levels of enantio- and diastereoselectivities (up to >20:1 dr and >99% ee). Furthermore, several representative transformations involving axial-to-central chirality transfer were conducted, affording useful structural motifs containing nonadjacent stereocenters in a diastereodivergent manner.
Deoxygenative Borylation of Secondary and Tertiary Alcohols
Friese, Florian W.,Studer, Armido
supporting information, p. 9561 - 9564 (2019/06/21)
Two different approaches for the deoxygenative radical borylation of secondary and tertiary alcohols are presented. These transformations either proceed through a metal-free silyl-radical-mediated pathway or utilize visible-light photoredox catalysis. Readily available xanthates or methyl oxalates are used as radical precursors. The reactions show broad substrate scope and high functional-group tolerance, and are conducted under mild and practical conditions.
