85048-22-2Relevant academic research and scientific papers
Nickel-Catalyzed Anionic Cross-Coupling Reaction of Lithium Sulfonimidoyl Alkylidene Carbenoids With Organolithiums
Bülow, Gerd,Baik, Mu-Hyun,Decker, Jürgen,Erdelmeier, Irene,Gais, Hans-Joachim,Park, Steve,Won, Joonghee
supporting information, (2020/02/28)
The mechanistic platform for a novel nickel0-catalyzed anionic cross-coupling reaction (ACCR) of lithium sulfonimidoyl alkylidene carbenoids (metalloalkenyl sulfoximines) with organometallic reagents is reported herein, affording substituted alkenylmetals and lithium sulfinamides. The Ni0-catalyzed ACCR of three different types of metalloalkenyl sulfoximines, including acyclic, axially chiral and exocyclic derivatives, with sp2 organolithiums and sp2 and sp3 Grignard reagents has been studied. The ACCR of metalloalkenyl sulfoximines with PhLi in the presence of the Ni0-catalyst and precatalyst Ni(PPh3)2Cl2 afforded alkenyllithiums, under inversion of configuration at the C atom and complete retention at the S atom. In a combination of experimental and DFT studies, we propose a catalytic cycle of the Ni0-catalyzed ACCR of lithioalkenyl sulfoximines. Computational studies reveal two distinctive pathways of the ACCR, depending on whether a phosphine or 1,5-cyclooctadiene (COD) is the ligand of the Ni atom. They rectify the underlying importance of forming the key Ni0-vinylidene intermediate through an indispensable electron-rich Ni0-center coordinated by phosphine ligands. Fundamentally, we present a mechanistic study in controlling the diastereoselectivity of the alkenyllithium formation via the key lithium sulfinamide coordinated Ni0-vinylidene complex, which consequently avoids an unselective formation of an alkylidene carbene Ni-complex and ultimately racemic alkenyllithium.
EFFICIENT OLEFINATION WITH α-ALKYL CYCLIC PHOSPHONAMIDES
Hanessian, Stephen,Bennani, Youssef L.,Leblanc, Yves
, p. 1411 - 1424 (2007/10/02)
A variety of acyclic and cyclic aldehydes and ketones can be converted into the corresponding alkylidene, benzylidene and methoxycarbonyl alkylidene derivatives by treatment with 1,3,2-diazaphospholidine-2-alkyl-1,3-dimethyl 2-oxides (α-alkyl cyclic phosphonamides) under mild conditions.This olefination method is particularly useful in the case of enolizable carbonyl compounds.
Stereoselective Synthesis of (Z)- and (E)-1,3-Alkadienes from Aldehydes Using Organotitanium and Lithium Reagents
Ikeda, Yoshihiko,Ukai, Junzo,Ikeda, Nobuo,Yamamoto, Hisashi
, p. 723 - 730 (2007/10/02)
titanium reagent generated easily from allyldiphenylphosphine condenses with aldehydes to give (Z)-1,3-alkadienes in a highly regio- and stereoselective manner.In contrast, lithiated allyldiphenylphosphine oxide condenses with aldehydes to give (E)-1,3-alkadienes directly and stereoselectively in good yield.Similarly, lithiated (1-buten-3-yl)diphenylphosphine oxide condenses with aldehydes to give (E)-3-methyl-1,3-alkadienes.
DIRECT, STEREOSELECTIVE SYNTHESIS OF EITHER E- OR Z-1,3-DIENES
Ukai, Junzo,Ikeda, Yoshihiko,Ikeda, Nobou,Yamamoto, Hisashi
, p. 4029 - 4032 (2007/10/02)
New synthetic methods for the preparation of Z- or E-1,3-dienes are described.
