- Sterically Demanding Oxidative Amidation of α-Substituted Malononitriles with Amines Using O2
-
An efficient amidation method between readily available 1,1-dicyanoalkanes and either chiral or nonchiral amines was realized simply with molecular oxygen and a carbonate base. This oxidative protocol can be applied to both sterically and electronically challenging substrates in a highly chemoselective, practical, and rapid manner. The use of cyclopropyl and thioether substrates support the radical formation of α-peroxy malononitrile species, which can cyclize to dioxiranes that can monooxygenate malononitrile α-carbanions to afford activated acyl cyanides capable of reacting with amine nucleophiles.
- Li, Jing,Lear, Martin J.,Hayashi, Yujiro
-
-
Read Online
- Synthesis and Properties of Some tert-Alkylmalonic Acid Derivatives
-
1,4-Addition of Grignard reagents to the alkylidenemalonic acid derivatives 1-8 affords the tert-alkyl malonic derivatives 9-18.The esters 9-17 give the acids 19-26 and from these the corresponding chlorides 27-34 are obtained.Bromination yields the bromo acids 35-36, the brominated acyl bromide 43, the bromonitrile 44, and the bromoacyl chlorides 37-42.The trimethylsilyl esters 50-52, the bis(2-bromoethyl) esters 53-54, the ethyl ester 14, and the tert-butyl ester 16 are brominated via the corresponding ester enolates giving the bromo esters 45-46 in pure form. - The dealkylation of malonic esters with chlorotrimethylsilane/sodium iodide has been carried out.
- Holmberg, Carl
-
p. 748 - 760
(2007/10/02)
-