Iridium Complex- Catalyzed Carbon-Carbon and Carbon-Heteroatom Bond Formation

铱配合物-催化碳-碳和碳-杂原子键的形成

基本信息

批准号：
16550099
负责人：
TAKEUCHI Ryo
金额：
$ 2.05万
依托单位：
Aoyama Gakuin University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

项目摘要

We have studied the following reactions.1)[Ir(cod)Cl]_2/DPPE-catalyzed allylic alkylation of 1,1-disubstituted-2,3-butadienyl acetates gives a product bearing a quaternary carbon center α to allene in high yield. The reaction is an efficient method for constructing a quaternary carbon center α to allene. The reaction proceeds via 1-methylene-3,3-disubstituted π-allyl iridium intermediate2)1,6-Enynes reacted with monoynes to give cyclohexadiene derivatives in the presence of a catalytic amount of [Ir(cod)Cl]_2/ligand. DPPE was most suitable for cycloaddition. Diastereoselective cycloaddition was also possible. In the absence of monoynes, 1,6-enynes cycloisomerized to (Z)-1-alkylidene-2-methylenecyclopentane derivatives. DPPF was most suitable for cycloisomerization. These results are the first examples of highly Z-selective cycloisomerization.3)[Ir(cod)Cl]_2/DPPE was found to be a new catalyst for the cycloaddition of α,ω-diynes with monoynes to give polysubstituted benzene derivatives … More in high yields. Internal monoynes as well as terminal monoynes could be used. The reaction tolerates a broad range of functional groups such as alcohol, amine, alkene, ether, halogen and nitrile. The reaction of 1,6-octadiyne derivatives with 1-alkynes gives ortho-products and meta-products. The regioselectivity could be controlled by the choice of ligand. The reaction using DPPE was meta-selective, with meta-selectivity of up to 82%. The reaction using DPPF was ortho-selective, with ortho-selectivity of up to 88%. We propose a mechanism to account for this regioselective cycloaddition. [Ir(cod)Cl]_2/DPPE also catalyzed the cycloaddition of α,ω-diynes with 2,5-dihydrofuran to give bicyclic cyclohexadiene derivatives. The reaction with 2,3-dihydrofuran and n-butyl vinyl ether gave benzene derivatives instead of cyclohexadiene derivatives. We also propose a mechanism to account for this novel aromatization that includes cleavage of the C-O bond.4)The stereochemistry of [Ir(cod)Cl]_2/P(OPh)_3-catalyzed allylic amination has been studied. The reaction of (R)-1-phenyl-2-propenyl carbonate with benzylamine gave (R)-allylic amine. The reaction was found to proceed with the retention of the stereochemistry. Less

我们研究了以下反应。1)[Ir(cod)Cl]_2/DPPE催化1,1-二取代-2,3-丁二烯基乙酸酯的烯丙基烷基化反应高产率地得到季碳中心α为丙二烯的产物该反应是构建季碳中心α至丙二烯的有效方法。该反应通过1-亚甲基-3,3-二取代的π-烯丙基进行。铱中间体2)1,6-烯炔在催化量的[Ir(cod)Cl]_2/配体存在下与单炔反应生成环己二烯衍生物，最适合于环加成反应，在不存在的情况下也可以进行非对映选择性环加成反应。单炔，1,6-烯炔环异构化为(Z)-1-亚烷基-2-亚甲基环戊烷衍生物最适合环化异构化。这些结果是高度Z选择性环化异构化的第一个例子。3)[Ir(cod)Cl]_2/DPPE被发现是一种。用于 α,ω-二炔与单炔环加成以高产率生成多取代苯衍生物的新型催化剂。该反应可耐受多种官能团，如醇、胺、烯烃、醚、卤素和腈。1,6-辛二炔衍生物与1-炔烃反应生成邻位产物和间位产物。 -产物的区域选择性可以通过配体的选择来控制。使用DPPE的反应是间位选择性的，间位选择性高达82%。使用 DPPF 的反应是邻位选择性的，邻位选择性高达 88%，我们提出了一种机制来解释这种区域选择性环加成反应。 2,5-二氢呋喃与2,3-二氢呋喃反应得到双环环己二烯衍生物。正丁基乙烯基醚产生苯衍生物而不是环己二烯衍生物。我们还提出了一种解释这种新型芳构化的机制，其中包括 C-O 键的断裂。4) [Ir(cod)Cl]_2/P(OPh) 的立体化学。研究了_3-催化的烯丙胺化(R)-1-苯基-2-丙烯基碳酸酯与苄胺的反应。 (R)-烯丙胺发现反应进行时立体化学保留较少。