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首页> 外文学位 >Palladium catalyzed thiocarbonylation and related reactions of functionally substituted alkenes and alkynes, allenes, and enynes.
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Palladium catalyzed thiocarbonylation and related reactions of functionally substituted alkenes and alkynes, allenes, and enynes.

机译：钯催化的硫代羰基化反应以及官能取代的烯烃与炔烃，丙二烯和烯炔的相关反应。

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摘要

A systematic investigation has been carried out on the palladium-catalyzed thiocarbonylation and related reactions of unsaturated substrates such as propargylic and allylic alcohols, 1,2- and 1,3-dienes, and conjugated enynes with thiols and carbon monoxide.; It has been first demonstrated that the reaction of allylic alcohols with thiols and CO in the presence of catalytic quantities of Pd(OAc) 2 (3 mol%), triphenylphosphine (12 mol%), and p-TsOH (5 mol%) leads to a novel reaction, namely thiocarbonylation, to afford β,γ-usaturated thiol esters in good to excellent yields. Other catalyst systems such as Pd 2(dba)3·CHCl3/PPh3/p-TsOH, Pd(PPh 3)4/p-TsOH, and Pd(OAC)2/dppb/ p-TsOH are also effective for this transformation. The thiocarbonylation reaction is believed to proceed via a η3-allylpalladium intermediate. The reaction occurs in a highly regioselective manner, at the least hindered allylic terminal carbon of the substrate, to give the products. The new carbonylation procedure was readily applied to a variety of allylic alcohols, and to both aromatic and aliphatic thiols.; Palladium (0) as well as palladium (II) complexes with added phosphine ligands catalyze the thiocarbonylation of propargylic compounds. Depending on the reaction conditions employed, the reaction can afford mono- and di-thioesters or β-thio-substituted γ-lactones as the principal products in good yields, respectively. Thus, in the presence of 3 mol% of Pd(OAC)2, 5 mol% of p-TsOH, and 12 mol% of PPh3, propargylic alcohols react with thiols in THF under 400 psi of carbon monoxide at 100°C to give monothioesters in excellent yields. β-Thio-α,β-unsaturated-γ-lactones can be prepared in high yields by the thiolactonization of propargylic alcohols using Pd(PPh3)4 as the catalyst and DME as the solvent. Propargylic mesylates undergo dithiocarbonylation when they are treated with catalytic amounts of Pd(PPh3)4. This reaction exclusively gives dithioesters under milder conditions (90°C, 400 psi).; A series of mono- and di-substituted allenes undergo direct thiocarbonylation with thiols and carbon monoxide to form the corresponding unsaturated thioesters in 73–94% isolated yields. This reaction requires catalytic quantities of Pd(OAC)2 (3 mol%) and triphenylphosphine (12 mol%) in THF under an atmosphere of CO (400 psi) at 100°C for 48 h. The reaction is believed to proceed via π-allylpalladium complex. The reaction exhibits high regioselectivity, in which the thiophenyl group adds to the less substituted double bond of allenes. (Abstract shortened by UMI.)
机译：对钯催化的硫代羰基化反应以及不饱和底物如炔丙醇和烯丙醇，1，2-和1，3-二烯，共轭炔与硫醇和一氧化碳的相关反应进行了系统的研究。首先证明了在催化量的Pd（OAc） 2 （3 mol％），三苯膦（12 mol％）和对-TsOH（5mol％）导致新的反应，即硫代羰基化，以良好至优异的产率提供β，γ-饱和的硫醇酯。其他催化剂体系，例如Pd 2 （dba） 3 ·CHCl 3 / PPh 3 / p-TsOH， Pd（PPh 3 ） 4 / p -TsOH和Pd（OAC） 2 / dppb / p -TsOH对这种转化也有效。硫羰基化反应被认为是通过 3 -烯丙基钯中间体进行的。该反应以高度区域选择性的方式发生，在底物的受阻最少的烯丙基末端碳上发生，从而得到产物。新的羰基化方法很容易应用于各种烯丙基醇以及芳族和脂族硫醇。具有添加的膦配体的钯（0）以及钯（II）配合物可催化炔丙基化合物的硫羰基化反应。取决于所采用的反应条件，该反应可以以高收率分别得到单和二硫代酸酯和β-硫代取代的γ-内酯作为主要产物。因此，在存在3mol％的Pd（OAC） 2 ，5mol％的 p -TsOH和12mol％的PPh 3 3 ） 4 为催化剂，通过炔丙醇的硫醇内酯化可以高收率地制备β-硫代α，β-不饱和γ-内酯。以二甲醚为溶剂。丙炔基甲磺酸酯在用催化量的Pd（PPh 3 ） 4 处理时会发生二硫代羰基化。该反应仅在温和的条件下（90°C，400 psi）得到二硫酯。一系列的单取代和双取代的烯基与硫醇和一氧化碳直接进行硫羰基化反应，形成相应的不饱和硫酯，分离产率为73-94％。该反应需要在100°C的CO（400 psi）气氛下于THF中催化量的Pd（OAC） 2 （3 mol％）和三苯膦（12 mol％）。据信该反应通过斜体π-烯丙基钯络合物进行。该反应表现出高的区域选择性，其中硫代苯基基团加成较少取代的丙二烯双键。 （摘要由UMI缩短。）

著录项

  • 作者

    Xiao, Wen-Jing.;

  • 作者单位

    University of Ottawa (Canada).;

  • 授予单位 University of Ottawa (Canada).;
  • 学科 Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2001
  • 页码 283 p.
  • 总页数 283
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 有机化学;
  • 关键词

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