Li Chun-Tian, Liu Hui, Yao Yun, Lu Chong-Dao
Xinjiang Technical Institute of Physics & Chemistry , Chinese Academy of Sciences , Urumqi 830011 , China.
School of Chemical Science and Technology , Yunnan University , Kunming 650091 , China.
Org Lett. 2019 Oct 18;21(20):8383-8388. doi: 10.1021/acs.orglett.9b03159. Epub 2019 Oct 8.
Treating chiral --butanesulfinyl ketimines with potassium hexamethyldisilazide (or potassium -butoxide) and methyl triflate gives -methylated --butanesulfinyl enamine intermediates that undergo stereoselective [2,3]-rearrangement to afford α-sulfenyloxy ketones with excellent enantiopurities. This cascade of enamination--methylation-rearrangement was even used to generate acyclic tertiary α-hydroxy ketones bearing two α-substituents showing negligible differences in bulkiness, such as methyl and ethyl groups.
用六甲基二硅氮基钾（或丁醇钾）和三氟甲磺酸甲酯处理手性丁烷亚磺酰基酮亚胺，得到α-甲基化的丁烷亚磺酰基烯胺中间体，该中间体发生立体选择性的[2,3]重排，得到对映体纯度优异的α-亚磺酰氧基酮。这种烯胺化-甲基化-重排的串联反应甚至被用于生成带有两个体积差异可忽略不计的α-取代基（如甲基和乙基）的无环叔α-羟基酮。
