DIRECTED DILITHIATION OF HEXAFLUOROCUMYL ALCOHOL - FORMATION OF A REAGENT FOR THE FACILE INTRODUCTION OF A STABILIZING BIDENTATE LIGAND IN COMPOUNDS OF HYPERVALENT SULFUR (10-S-4), PHOSPHORUS (10-P-5), SILICON (10-SI-5), AND IODINE (10-I-3)
DIRECTED DILITHIATION OF HEXAFLUOROCUMYL ALCOHOL - FORMATION OF A REAGENT FOR THE FACILE INTRODUCTION OF A STABILIZING BIDENTATE LIGAND IN COMPOUNDS OF HYPERVALENT SULFUR (10-S-4), PHOSPHORUS (10-P-5), SILICON (10-SI-5), AND IODINE (10-I-3)
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DOI：
10.1021/jo00319a001
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发表时间：
1981-01-01
影响因子：
3.6
通讯作者：
MARTIN, JC
中科院分区：
文献类型：
--
作者：
PEROZZI, EF;MICHALAK, RS;MARTIN, JC
1，1，1，3，3，3-六氟-2-苯基-2-丙醇（RFOH）与仲丁基锂或正丁基锂/四甲基乙二胺（TMEDA）的反应提供了3，其是一种用于容易引入双齿配体的试剂，其在稳定非金属元素的较高配位态方面特别有效。该试剂用于制备一系列螺环化合物，其中这些配体中的两个连接到高价硅（阴离子10-Si-5物质6a-d，13）、磷（10-P-5磷氧化物盐8）、硫（非常不反应的硫烷，10-S-4物质9）或碘（10-1-3物质15）。3与SiCl反应，得到预期的螺硅烷12，一种8-S-4物质，其与各种亲核试剂反应，得到五配位硅（10-Si-5）物质。例如，12与苯基锂反应得到6a。弱得多的亲核试剂4-（二甲氨基）吡啶产生稳定的络合物，其涉及氮对硅的攻击。3与元素硫反应得到二硫化物二醇7a。与1，2-二溴乙烷或元素溴反应得到溴代醇11 a，而I2与3反应得到碘代醇11b。
The reaction of l, l, l, 3, 3, 3-hexafluoro-2-phenyl-2-propanol (RFOH) with either sec-butyllithium or n-butyl-lithium/IVJVrZV'JV'-tetramethylethylenediamine (TMEDA) provides 3, a reagent for the facile introduction of a bidentate ligand which is particularly effective in stabilizing the higher coordination states of nonmetallic elements. This reagent is used to prepare a series of spiro compounds in which two of these ligands are attached to hypervalent silicon (anionic lO-Si-5 species 6a-d, 13), phosphorus (10-P-5 phosphoranoxide salt 8), sulfur (the very unreactive sulfurane, 10-S-4 species 9), or iodine (10-1-3 species 15). Reaction of 3 with SiCL, gives the expected spirosilane, 12, an 8-SÍ-4 species which reacts with a variety of nucleophiles to give pentacoordinate silicon (lO-Si-5) species. For example, reaction of 12 with phenyllithium gives 6a. The much weaker nucleophile 4-(dimethylamino) pyridine gives a stable complex which involves nitrogen attack at silicon. Reaction of 3 with elemental sulfur gives disulfide diol 7a. Reaction with either 1, 2-dibromoethane or elemental bromine gives bromo alcohol 11a, while I2 reacts with 3 to give iodo alcohol lib.