Thorat Rakesh G, Brooks Bailey A, Nichols Brandon, Harned Andrew M
Texas Tech University, Department of Chemistry & Biochemistry, 1204 Boston Ave., Lubbock, TX, 79409-1061, USA.
Tetrahedron. 2018 Dec 20;74(51):7277-7281. doi: 10.1016/j.tet.2018.10.066. Epub 2018 Nov 2.
Transition met al catalysis has enabled the highly stereoselective and protecting group-free synthesis of the C14-C23 fragment of the apoptosis-inducing natural products biselyngbyolide A and B. A Pd-catalyzed Stille reaction between a vinyl stannane and a crotyl carbonate formed the skipped diene with complete control of the the trisubstituted bond and excellent control over the branched/linear products. A Cu-catalyzed Stahl oxidation was used to form the requisite aldehyde needed for a Ag-catalyzed asymmetric allylation. The latter provided the final fragment with excellent stereochemical control.
过渡金属催化实现了对诱导凋亡的天然产物双鞘丝藻内酯A和B的C14 - C23片段进行高度立体选择性且无需保护基团的合成。乙烯基锡烷与巴豆基碳酸酯之间的钯催化施蒂勒反应形成了具有三取代键完全可控以及对支链/直链产物有出色控制的跳跃二烯。铜催化的施塔尔氧化反应被用于形成银催化不对称烯丙基化所需的醛。后者以出色的立体化学控制提供了最终片段。
