A Pd-Catalyzed Site-Controlled Isomerization of Terminal Olefins
作者:Wenlong Ren、Fei Sun、Jianxiao Chu、Yian Shi
DOI:10.1021/acs.orglett.0c00168
日期:2020.3.6
An effective Pd-catalyzed isomerization of olefins with 2-PyPPh2 as the ligand is described. A wide variety of trans-2-olefins bearing various functional groups can be obtained with high regio- and stereoselectivity under mild reaction conditions. The ligand is crucial for the reaction.
Enantioselective C–C cross-coupling of unactivated alkenes
作者:Zi-Chao Wang、Xiaohua Luo、Jia-Wen Zhang、Chen-Fei Liu、Ming Joo Koh、Shi-Liang Shi
DOI:10.1038/s41929-023-01037-9
日期:——
carbonickelation and in situ trapping with nucleophiles enable efficient hydrofunctionalization and dicarbofunctionalization of unactivated alkenes in a directing group-free manner. Nickelcatalysts bearing bulky C2-symmetric chiral N-heterocyclic carbene ligands were crucial for attaining high reactivity and selectivity. This strategy offers a general, modular and divergent platform for rapidly upgrading
几十年来,金属催化的交叉偶联在现代化学合成中发挥着核心作用。未活化的烯烃,包括轻质烯烃,在石油工业中被大规模生产,是制备药物、农用化学品和材料的理想起始材料。然而,未活化烯烃的对映选择性交叉偶联仍然是一个具有挑战性的长期目标。在这里,我们报道了未活化烯烃与芳基(或烯基)三氟甲磺酸酯和有机金属(或还原剂)的高度对映和区域选择性三组分交叉偶联,以构建不同的 C sp 3通过镍催化形成立构中心。具体来说,选择性碳镍化和亲核试剂的原位捕获能够以无导向基团的方式对未活化的烯烃进行有效的氢官能化和二碳官能化。带有大体积C 2对称手性N-杂环卡宾配体的镍催化剂对于获得高反应性和选择性至关重要。该策略提供了一个通用、模块化和发散的平台,用于将原料烯烃快速升级为各种增值分子,并有望激发其他具有挑战性的对映选择性烯烃交叉偶联的开发。
Catalytic Asymmetric Allylic and Homoallylic Diamination of Terminal Olefins via Formal C−H Activation
作者:Haifeng Du、Baoguo Zhao、Yian Shi
DOI:10.1021/ja8027394
日期:2008.7.1
This paper describes a catalyticasymmetric diamination process for terminal olefins at allylic and homoallylic carbons via formal C-H activation using di-tert-butyldiaziridinone as nitrogen source with a catalyst generated from Pd2(dba)3 and chiral phosphorus amidite ligand. A wide variety of readily available terminal olefins can be effectively diaminated in good yields with high regio-, diastereo-
Tricyclicdicarboximides representatively prepared by the Diels-Alder condensation of a cyclic diene such as cycloheptatriene, cyclooctatetraene and the like with a dienophile such as substituted N-phenylmaleimide and the like are disclosed having pharmaceutical utility as minor tranquilizers and anti-convulsants. Also disclosed are processes for the preparation of such tricyclicdicarboximides; pharmaceutical compositions comprising such compounds and their salt, ester and amide derivatives; and methods of treatment comprising administering such compounds and compositions.