Silyl Migrations

Abstract

Introduction 1,2‐Silyl Migrations 1,3‐Silyl Migrations 1, N ‐Silyl Migrations ( n ≥ 4)

Diazoalkanes in Low-Coordinate Iron Chemistry: Bimetallic Diazoalkyl and Alkylidene Complexes of Iron(II)

“…This type of isomerization to a bridging diazoalkyl ligand is unknown for transition metal systems, though it has been seen with lanthanides and uranium. 32–35 The known aluminum complex [(CH(SiMe 3 ) 2 )Al(μ-NNC(SiMe 3 ))] 2 has the same CNN bridging core, but its trimethylsilyl group is coordinated to carbon. 31 …”

Synthesis and activity of the archazolid western hemisphere

“…Reduction of the ketone with NaBH 4 gave the corresponding alcohol with >10 : 1 diastereoselectivity as determined by NMR analysis. 19 After some experimentation, it was found that methylation of the newly generated hydroxyl-group could be performed on gram scale by deprotonation with a freshly prepared precooled solution of LiHMDS followed by alkylation with methyl triflate (MeOTf) at -78 • C. Allowing the reaction mixture to warm resulted in a significant amount of 1,3-silyl migration 20 and a mixture of products. Selective removal of the primary TBS-group 21 in 12 and oxidation with Dess-Martin periodinane 22 then completed a synthesis of aldehyde 6.…”