Chemistry of N,N-bis(silyloxy)enamines 7. Quaternization of tertiary amines and nitrogen-containing heterocycles by N,N-bis(silyloxy)enamines

Abstract

Coupling of N,N bis(silyloxy)enamines with tertiary amines and nitrogen containing het erocycles affording the corresponding functionalized ammonium or iminium salts was studied. The area of its application was determined, and optimal procedures for the synthesis of the target products were proposed. The mechanism including the formation of conjugated nitroso alkene or a silylnitrosonium cation as key intermediates is discussed.

Metal-Involving Synthesis and Reactions of Oximes

“…Synthetic routes to cyclic oxime ethers, particularly from bis­(oxy)­enamines (which are typically prepared from nitro compounds; , Scheme , c and f) were comprehensively reviewed in 2011; below, we focus on reactions leading to the acyclic oxime species. These reactions are typically promoted by the R 3 Si + species, − or they proceed even in the absence of a promoter, and lead to oxime ethers XCR 1 R 2 C­(R 3 )NOE (g) functionalized at the α-position or to appropriate oximes (X = amino, , azido, , hetaryl, oxy, , chloride; Scheme ). The application of cobalt­(II) species as catalysts is reported to provide high-yield syntheses of acyclic α-halo and α-nitroxy oxime ethers.…”

The Chemistry ofN,N-Bis(siloxy)enamines. Part 8.A General Method for the Preparation of α-Azido Oximes from Aliphatic Nitro Compounds

“…3,4 The unique ability of BENA, to interact at the b-position with some electrophiles 5,6 as well as with various nucleophiles, [7][8][9][10][11][12][13] can be used for the functionalization of the bcarbon atom of readily available initial ANC. Earlier, we developed this novel strategy for the synthesis of various a-functionalized 1,[7][8][9][10]13 or modified 11,12 oximes from the simplest ANC.…”