Stoichiometric reactions of enamines derived from diphenylprolinol silyl ethers with nitro olefins and lessons for the corresponding organocatalytic conversions - A survey

Dieter Seebach, Xiaoyu Sun, Marc Olivier Ebert, W. Bernd Schweizer, Nirupam Purkayastha, Albert K. Beck, Jörg Duschmalé, Helma Wennemers, Takasuke Mukaiyama, Meryem Benohoud, Yujiro Hayashi, Markus Reiher

研究成果: Article査読

63 被引用数 (Scopus)

抄録

The stoichiometric reactions of enamines prepared from aldehydes and diphenyl-prolinol silyl ethers (intermediates of numerous organocatalytic processes) with nitro olefins have been investigated. As reported in the last century for simple achiral and chiral enamines, the products are cyclobutanes (4 with monosubstituted nitro-ethenes), dihydro-oxazine N-oxide derivatives (5 with disubstituted nitro-ethenes), and nitro enamines derived from γ-nitro aldehydes (6, often formed after longer reaction times). The same types of products were shown to be formed, when the reactions were carried out with peptides H-Pro-Pro-Xaa-OMe that lack an acidic H-atom. Functionalized components such as alkoxy enamines, nitro-acrylates, acetamido-nitro-ethylene, or hydroxylated nitro olefins also form products carrying the diphenyl-prolinol silyl ether as a substituent. All of these products must be considered intermediates in the corresponding catalytic reactions; the investigation of their chemical properties provided useful hints about the rates, the conditions, the catalyst resting states or irreversible traps, and/or the limitations of the corresponding organocatalytic processes. High-level DFT and MP2 computations of the structures of alkoxy enamines and thermodynamic data of a cyclobutane dissociation are also described. Some results obtained with the stoichiometrically prepared intermediates are not compatible with previous mechanistic proposals and assumptions.

本文言語English
ページ(範囲)799-852
ページ数54
ジャーナルHelvetica Chimica Acta
96
5
DOI
出版ステータスPublished - 2013 5月
外部発表はい

ASJC Scopus subject areas

  • 触媒
  • 生化学
  • 創薬
  • 物理化学および理論化学
  • 有機化学
  • 無機化学

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