STEREOCHEMISTRY OF REACTIONS AT CARBON-TRANSITION METAL SIGMA BONDS - (CH3)3CCHDCHDFE(CO)2C5H5
STEREOCHEMISTRY OF REACTIONS AT CARBON-TRANSITION METAL SIGMA BONDS - (CH3)3CCHDCHDFE(CO)2C5H5
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DOI：
10.1021/ja00816a025
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发表时间：
1974-01-01
影响因子：
15
通讯作者：
WHITESID.GM
中科院分区：
文献类型：
--
作者：
BOCK, PL;BOSCHETT.DJ;WHITESID.GM
方便，立体选择性合成苏式和…？R> 7-氯-3，3-二甲基丁-1-醇-1，2-醇-2（1）。1的对溴苯磺酸酯与CsH_3FeCCO_3、MgBr、-Li或-Na反应，生成环戊二烯基二羰基铁赤型和？Areo-3，3-二甲基丁基-l，2-d2（赤型-和苏型-2），在碳上具有> 95%的构型转化。2在戊烷、氯仿、二硫化碳和二甲基甲酰胺中的溴化反应，以及在二硫化碳中的碘化反应，都发生了> 90%的碳构型转化。2与三苯基膦、叔丁基异氰化物、溴（在甲醇中）、氧、铈（IV）离子或氯（在氯仿中）的反应导致4，4-二甲基戊酸-2，1_f 2酸的衍生物，其在碳上具有> 90%的构型保留。2与二氧化硫在各种溶剂中反应产生二氧化硫插入产物（CH 3）3CCHDCHDS 02 Fe（CO）2Cp，在碳上具有> 95%的构型转化。乙炔二羧酸二甲酯插入到2的碳-铁键中，在碳上保持> 80%的构型。2的热分解产生3，3_二甲基-1-丁烯的一系列同位素取代的衍生物。并对结果的机理意义进行了讨论。
Convenient, stereoselective syntheses of threo-and¡? r> 7/iro-3, 3-dimethylbutan-l-oI-/, 2-i/2 (1) are described. Reaction of the p-bromobenzenesulfonate esters of 1 with CsHsFeCCOjüMgBr,-Li, or-Na yields ir-cyclopentadienyldicarbonyliron erythro-and? Areo-3, 3-dimethylbutyl-/, 2-d2 (erythro-and threo-2) with> 95% in-version of configuration at carbon. Bromination of 2 in pentane, chloroform, carbon disulfide, and dimethylformamide, and iodination in carbon disulfide, all takeplace with> 90% inversion of configuration at carbon. Reaction of 2 with triphenylphosphine, zm-butyl isocyanide, bromine (in methanol), oxygen, cerium (IV) ion, or chlorine (in chloroform) leads to derivatives of 4, 4-dimethylpentanoic-2, J-flf2 acid with> 90% retention of configuration at carbon. Reaction of 2 with sulfur dioxide in a variety of solvents yields the product of sulfur dioxide insertion,(CH3) 3CCHDCHDS02Fe (C0) 2Cp, with> 95% inversion of configuration at carbon. Insertion of dimethyl acety-lenedicarboxylate into the carbon-iron bond of 2 takes place with> 80% retention of configuration at carbon. Thermal decomposition of 2 produces a range of isotopicaUy substituted derivatives of 3, 3-dimethyl-l-butene. The mechanistic significance of the results is discussed.