Total Synthesis of Natural Enantiomers of Heliespirones A and C via the Diastereoselective Intramolecular Hosomi-Sakurai Reaction
详细信息 查看全文
- 作者：Akari Miyawaki ; Daisuke Kikuchi ; Masu Niki ; Yuki Manabe ; Makoto Kanematsu ; Hiromasa Yokoe ; Masahiro Yoshida ; Kozo Shishido
- 刊名：The Journal of Organic Chemistry
- 出版年：2012
- 出版时间：September 21, 2012
- 年：2012
- 卷：77
- 期：18
- 页码：8231-8243
- 全文大小：449K
- 年卷期：v.77,no.18(September 21, 2012)
- ISSN：1520-6904
文摘
A full account of the development of a novel type of the intramolecular Hosomi-Sakurai reactions of the substrates with a p-benzoquinone and an allylsilane moieties connected by an ether linkage is described. This transformation proceeds via an addition鈥揺limination sequence and provides the products with two stereogenic centers through a 1,3(or 1,4)-asymmetric induction in good to excellent diastereoselectivities. A reasonable mechanistic possibility for the reaction, determination of the stereochemistry for the product, and scope and limitation of the transformation are also discussed. The methodology developed here can successfully be applied to the enantiocontrolled total synthesis of the natural enantiomers of (鈭?-heliespirone A and (+)-heliespirone C, which have been isolated from sunflower Helianthus annuus L. as allelochemicals.