title: Sakurai reaction of 3,3-bis(silyl) silyl enol ethers with acetals involving selective desilylation of the geminal bis(silane). Concise synthesis of nematocidal oxylipid.
abstract: 3,3-Bis(silyl) silyl enol ethers have been shown to exhibit predominantly Sakurai reactivity, rather than Mukaiyama aldol reactivity, in their Lewis acid promoted reactions with acetals. Starting from a geminal bis(silyl) moiety consisting of two different silyl groups, such as SiMe(3) and SiMe(2)Ph, the SiMe(3) is selectively eliminated to give monoprotected E- vinylsilyl diols with good to excellent syn-diastereoselectivity. This reaction also underpinned a synthesis of the nematocidal oxylipid from Notheia anomala, demonstrating the attractive bifunctionality of geminal bis(silanes).
authors: Key Laboratory of Drug-Targeting of Education Ministry and Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041, P. R. China.
authors: Linjie
authors: L
authors: Li
authors: Xincui
authors: X
authors: Ye
authors: Ya
authors: Y
authors: Wu
authors: Lu
authors: L
authors: Gao
authors: Zhenlei
authors: Z
authors: Song
authors: Zhiping
authors: Z
authors: Yin
authors: Yongjin
authors: Y
authors: Xu
mesh_terms: D000080:Acetals / Q000737:chemistry*; D000447:Aldehydes / Q000737:chemistry; D000969:Antinematodal Agents / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D020650:Combinatorial Chemistry Techniques; D058116:Lewis Acids / Q000737:chemistry; D015394:Molecular Structure; D054883:Oxylipins / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D000459:Phaeophyceae / Q000737:chemistry; D012821:Silanes / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D013237:Stereoisomerism
chemical_list: D000080:Acetals; D000447:Aldehydes; D000969:Antinematodal Agents; D058116:Lewis Acids; D054883:Oxylipins; D012821:Silanes; C116609:3-hydroxybutanal