Waetzig Joshua D, Hanson Paul R
Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Lawrence, Kansas 66045, USA.
Org Lett. 2008 Jan 3;10(1):109-12. doi: 10.1021/ol7025944. Epub 2007 Dec 7.
A phosphate tether approach to the C1-14 subunit of dolabelide is described. The phosphate tether serves a multifaceted role mediating several processes, including (i) diastereotopic differentiation via RCM, (ii) selective CM by imparting Type III behavior to the exocyclic olefin, (iii) regioselective hydrogenation, and (iv) regioselective Pd(0)-catalyzed reductive opening of the bicyclic phosphate. Overall, this strategy uses orthogonal protecting- and leaving-group properties innate to phosphate esters to rapidly assembly the titled subunit.
描述了一种用于多拉贝肽C1-14亚基的磷酸酯连接方法。磷酸酯连接起着多方面的作用,介导多个过程,包括:(i)通过复分解反应进行非对映异构分化;(ii)通过赋予环外烯烃III型行为实现选择性交叉复分解反应;(iii)区域选择性氢化;以及(iv)区域选择性钯(0)催化的双环磷酸酯的还原开环。总体而言,该策略利用磷酸酯固有的正交保护基和离去基团特性来快速组装目标亚基。