1463-04-3Relevant articles and documents
Catalytic Enantioselective Synthesis of β-Allenyl Boronic Esters by Conjunctive Cross-Coupling with Propargylic Carbonates
Aparece, Mark D.,Hu, Weipeng,Morken, James P.
, p. 11381 - 11385 (2019)
Enantioselective conjunctive cross-coupling with propargylic carbonates affords β-boryl allenes as the reaction product. The reaction is found to proceed through the intermediacy of dimethoxyboronate complexes that are generated in situ by a strain-induce
Diverse Pathways in Catalytic Reactions of Propargyl Aryldiazoacetates: Selectivity between Three Reaction Sites
Qiu, Huang,Deng, Yifan,Marichev, Kostiantyn O.,Doyle, Michael P.
, p. 1584 - 1590 (2017)
Three catalyst-dependent divergent reaction pathways for reactions of propargyl aryldiazoacetates are disclosed. Transition metal catalysts including those of rhodium(II), palladium(0 and II), silver(I), mercury(II), copper(I and II), platinum(II), and cationic gold(I) are effective for reactions that proceed through dinitrogen extrusion, carbene/alkyne metathesis, and aromatic substitution to form fused indeno-furanones, and use of tetrakis(acetonitrile)copper(I) provides indeno-furanones in the highest product yields. A Lewis acid catalyzed pathway that forms furan-2-ones is uncovered with FeCl3, ZnBr2, and BF3·Et2O as catalysts that proceed through activation of the aryldiazoacetate ester for arylpropargyl cation dissociation followed by recombination through cation addition to the diazo carbon. Neutral gold catalysts selectively activate the triple bond of propargyl aryldiazoacetates, resulting in the formation of allenic aryldiazoesters that further undergo uncatalyzed rearrangement.
Electrochemistry enabled selective vicinal fluorosulfenylation and fluorosulfoxidation of alkenes
Jiang, Yimin,Shi, Zhaojiang,Wu, Jinnan,Wu, Shaofen,Ye, Keyin,Yu, Yi,Yuan, Yaofeng
supporting information, (2021/11/17)
Both sulfur and fluorine play important roles in organic synthesis, the life science, and materials science. The direct incorporation of these elements into organic scaffolds with precise control of the oxidation states of sulfur moieties is of great significance. Herein, we report the highly selective electrochemical vicinal fluorosulfenylation and fluorosulfoxidation reactions of alkenes, which were enabled by the unique ability of electrochemistry to dial in the potentials on demand. Preliminary mechanistic investigations revealed that the fluorosulfenylation reaction proceeded through a radical-polar crossover mechanism involving a key episulfonium ion intermediate. Subsequent electrochemical oxidation of fluorosulfides to fluorosulfoxides were readily achieved under a higher applied potential with the adventitious H2O in the reaction mixture.
Stereo- And Regioselective cis-Hydrophosphorylation of 1,3-Enynes Enabled by the Visible-Light Irradiation of NiCl2(PPh3)2
Hou, Hong,Zhou, Bing,Wang, Jiawei,Zhao, Dengyang,Sun, Duhao,Chen, Xiaoyun,Han, Ying,Yan, Chaoguo,Shi, Yaocheng,Zhu, Shaoqun
supporting information, p. 2981 - 2987 (2021/05/05)
Described herein is a stereo- and regioselective cis-hydrophosphorylation reaction of the internal alkyne of 1,3-enynes that accesses various 1,3-dienes in good isolated yields. The visible-light irradiation of NiCl2(PPh3)2 allows the generation of highly reactive nickel(II)-phosphorus species that subsequently migrate into the internal alkyne of the 1,3-enynes and protonate the resulting vinyl nickel species, leading to various phosphinoyl 1,3-butadienes under mild reaction conditions.
