Stereocontrolled Synthesis of Angularly Fused Tricyclic Ring Systems by Means of 1-Metalla-1,3,5-hexatrienes (M=Cr, W)
作者:He-Ping Wu、Rudolf Aumann、Roland Fröhlich、Birgit Wibbeling
DOI:10.1002/1521-3765(20020215)8:4<910::aid-chem910>3.0.co;2-t
日期:2002.2.15
An efficient pathway for the stereocontrolled synthesis of functionalized, angularly fused tricyclic ring systems from readily available (1-alkynyl)carbene complexes [(OC)(5)M=C(OEt)C(triple bond)CR] (M=Cr, W; R=Ph, c-C(6)H(9)) is described. The synthesis involves the formation of a 1-metalla-1,3,5-hexatriene from the (1-alkynyl)carbene tungsten complex [(OC)(5)W=C(OEt)C(triple bond)C-c-C(6)H(9)] and
从容易获得的(1-炔基)卡宾配合物[(OC)(5)M = C(OEt)C(三键)CR](M = Cr, W; R = Ph,cC(6)H(9))被描述。合成涉及从(1-炔基)卡宾钨络合物[(OC)(5)W = C(OEt)C(三键)CcC(6)形成1-金属1,3,5-己三烯H(9)]和仲胺,及其热诱导的pi环化反应生成四氢茚,然后进行自发异构化为另一种四氢茚。这些四氢茚与(1-炔基)卡宾络合物[(OC)(5)M = C(OEt)C(三键)CPh](M = Cr,W)衍生的吡喃-2-亚烷基络合物的缩合反应顺利进行角稠合三环系统,其重排可能会产生螺(cyclopentane-1,1-茚满)作为副产品。该合成具有很高的通用性,可用于形成各种环系统,例如类固醇型环骨架。