Ti(OiPr)₄-Mediated Multicomponent Reactions Involving Triple Additions to Isonitrile Carbon Atoms

Abstract

Double addition of Grignard reagents to isonitriles was achieved in the presence of stoichiometric amounts of [Ti(OiPr)]. Functionalized isonitrile components were obtained in situ via lithiation of chiral and achiral 2-oxazolines, and the resulting amidomethyltitanium intermediate further reacted with a range of electrophiles. The established multicomponent procedure gave rise to highly substituted 2-aminomorpholines, acyclic diamino alcohols, and prenylated amino alcohols via straightforward synthetic protocols.

Tetracoordinate Boron Intermediates Enable Unconventional Transformations

“…29 Isocyanides with C−N triple bonds can be inserted twice, mediated by the transition metal to obtain a secondary amine. 30 As part of our continuous interest in the transformations of organoboron compounds under transition metalfree conditions, we achieved a multimigration reaction of tetracoordinate isocyanide boron intermediates derived from isocyanides and arylboronic acids to deliver a diarylmethanamine, 31 which is widely found in numerous pharmaceuticals, bioactive molecules, 32 and ligands 33 (Scheme 15). To our delight, the reaction of isocyanides with arylboronic acids or cyclic arylboronic anhydrides proceeded smoothly under basic conditions, allowing the formation of diarylmethanamine 36 or 9H-fluorene-9-amine 37 in moderate to good yields.…”

“…Isocyanides with C–N triple bonds can be inserted twice, mediated by the transition metal to obtain a secondary amine . As part of our continuous interest in the transformations of organoboron compounds under transition metal-free conditions, we achieved a multimigration reaction of tetracoordinate isocyanide boron intermediates derived from isocyanides and arylboronic acids to deliver a diarylmethanamine, which is widely found in numerous pharmaceuticals, bioactive molecules, and ligands (Scheme ).…”

Efficient Synthesis of Diarylmethanamines via Transition-Metal-Free Double-Insertive Coupling of Isocyanides with Arylboronic Acids

“…鉴于药物合成中金 属残留问题, 发展无过渡金属参与的策略, 实现双芳基 甲基胺类化合物的构建仍十分必要. 近日, 华侨大学/福 州大学材料科学与工程学院宋秋玲课题组与南方科技 大学化学系余沛源课题组 [6] [7] 和异氰-硼 "ate"复合物 1,2-迁移的启发 [8]…”