Diastereoselective Osmium-catalyzed Vicinal Oxyamination of Acyclic Allylic Alcohol Derivatives
作者:Masruri、Nicholas Kanizaj、Malcolm D. McLeod
DOI:10.1002/chir.22256
日期:2014.11
The osmium‐catalyzed oxyamination of chiral acyclic allylic alcohol derivatives bearing mono‐ and 1,1‐di‐substituted double bonds with benzyl N‐(4‐tosyloxy)carbamate proceeds with high regioselectivity and moderate levels of diastereoselectivity favoring the anti product. The observed stereoselectivity shows a clear and systematic trend with anti:syn ratios increasing in line with the size of substituent
带有N-(4-甲苯磺酰氧基)氨基甲酸苄酯的带有单和1,1-二取代双键的手性无环烯丙基醇衍生物的催化氧化胺化具有较高的区域选择性和适度的非对映选择性,有利于反产物。观察到的立体显示有明显的,系统的趋势防:SYN比例随烯丙基立体中心和双键α-碳上的取代基大小增加而增加。立体诱导与Kishi经验法则所预测的非对映选择性以及先前报道的for催化的烯丙醇衍生物二羟基化的过渡态模型相一致。相反,在所检查的情况下,带有三取代双键的烯丙基醇衍生物在氧胺化反应中显示出低的反应性或没有反应性,从而以低产率提供了合成产物。手性26:724–733,2013。©2013 Wiley Periodicals,Inc.