Gold- or Platinum-Catalyzed Synthesis of Sulfur Heterocycles: Access to Sulfur Ylides without Using Sacrificial Functionality
Gold- or Platinum-Catalyzed Synthesis of Sulfur Heterocycles: Access to Sulfur Ylides without Using Sacrificial Functionality
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DOI：
10.1002/anie.200904309
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发表时间：
2009-01-01
影响因子：
16.6
通讯作者：
Albrecht, Sebastien J-C
中科院分区：
文献类型：
--
作者：
Davies, Paul W.;Albrecht, Sebastien J-C
硫叶立德是有效的反应单元，其在合成化学中用于各种强大的碳-碳和碳-杂原子键形成反应。[1]叶立德的经典制备取决于“牺牲官能团”的使用：离去基团被硫化物置换，随后区域选择性地去质子化所得锍盐[Eq. (1)][2]或用金属卡宾处理硫化物，金属卡宾通过重氮化合物的分解而损失分子氮形成[Eq.②]。[3]这种方法的合成效率也受到引入前体部分所需的操作的不利影响。因此，这些策略对试剂使用、废物产生和官能团耐受性的负面影响降低了叶立德化学的吸引力，因此，通过不依赖于使用牺牲官能团的方法制备硫叶立德具有潜在的吸引力。[4]为此，我们最近建立了一个计划，探索在贵金属催化下从炔直接获得叶立德。在我们最初的研究中，我们报道了炔丙基羧酸酯的分子间耦合，
Sulfur ylides are potent reactive units which are utilized in synthetic chemistry for a variety of powerful carbon–carbon and carbon–heteroatom bond-forming reactions.[1] The classical preparation of ylides depend on the use of “sacrificial functionality”: a leaving group is displaced by a sulfide with subsequent regioselective deprotonation of the resulting sulfonium salt [Eq.(1)];[2] or a sulfide is treated with a metal carbene, which is formed by the decomposition of a diazo compound with loss of molecular nitrogen [Eq.(2)].[3] The synthetic efficiency of such processes is also adversely affected by the manipulations required to introduce the precursor moiety. Consequently, the appeal of ylide chemistry is diminished by the negative implications of these strategies on reagent usage, waste production, and functional group tolerance.The preparation of sulfur ylides by methods which do not depend on the use of sacrificial functionality are therefore potentially attractive.[4] To this end, we recently established a program to explore direct access to ylides from alkynes under noble-metal catalysis. In our initial study we reported the intermolecular coupling of propargylic carboxylates and