18181-05-0Relevant academic research and scientific papers
Manganese-Catalyzed anti-Selective Asymmetric Hydrogenation of α-Substituted β-Ketoamides
Ding, Kuiling,Han, Zhaobin,Wang, Zheng,Zhang, Linli
supporting information, p. 15565 - 15569 (2020/07/06)
A Mn-catalyzed diastereo- and enantioselective hydrogenation of α-substituted β-ketoamides has been realized for the first time under dynamic kinetic resolution conditions. anti-α-Substituted β-hydroxy amides, which are useful building blocks for the synthesis of bioactive molecules and chiral drugs, were prepared in high yields with excellent selectivity (up to >99 percent dr and >99 percent ee) and unprecedentedly high activity (TON up to 10000). The origin of the excellent stereoselectivity was clarified by DFT calculations.
Enolboration. 7. Dicyclohexyliodoborane, a Highly Stereoselective Reagent for the Enolboration of Tertiary Amides. Effects of Solvent and Aldolization Temperature on Stereochemistry in Achieving the Stereoselective Synthesis of either Syn or Anti Aldols
Ganesan, Kumaraperumal,Brown, Herbert C.
, p. 7346 - 7352 (2007/10/02)
A highly stereoselective enolboration of tertiary amides has been accomplished for the first time with dicyclohexyliodoborane, Chx2BI.A systematic study of the enolboration of representative N,N-dialkylpropionamides (CH3CH2CONR'2) with Chx2BI in the presence of various tertiary amines of variable steric requirements revealed an unusual aldol stereoselectivity in different solvents and at different aldolization temperatures.Both the nature of solvent and the aldolization temperature influence the stereochemistry of enolboration, with the solvent effect being greater than that of the temperature.Aliphatic and alicyclic hydrocarbon solvents favor formation of the syn aldols from the enol borinates by aldolization at lower temperature (-78 deg C), whereas most of the other solvents examined, such as aromatic and chlorinated aliphatic solvents, favor formation of the anti aldols by aldolization at relatively higher temperatures (0 or 25 deg C).The remarkable effects of both temperature and solvent in the case of tertiary amides raise a question about the validity of the previously assumed constancy of the Z to syn and E to anti relationship, suggesting either a possible isomerization of enol borinates with temperature or a different aldolization transition state with different solvent.While the effect of stric requirements of the dialkylamino group of the tertiary amide does not contribute significantly to the stereochemistry, that of the amine exerts a considerable influence.The present study establishes a simple procedure for the stereoselective synthesis of either syn or anti aldols from representative tertiary amides merely by changing the solvent and the aldolization temperature.
