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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。该反应是构建丙二烯季碳中心α的有效方法。该反应通过1-亚甲基-3,3-二取代的π-烯丙基铱中间体2)1,6-烯炔在催化量的[Ir(cod)Cl]_2/配体存在下与单炔反应进行，得到环己二烯衍生物。 DPPE最适合环加成。非对映选择性环加成也是可能的。在不存在单炔的情况下，1,6-烯炔环异构化为(Z)-1-亚烷基-2-亚甲基环戊烷衍生物。 DPPF最适合环化异构化。这些结果是高度 Z 选择性环异构化的第一个例子。3)[Ir(cod)Cl]_2/DPPE 被发现是一种新的催化剂，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。可以使用内部单炔以及末端单炔。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-炔烃的反应产生邻位产物和间位产物。区域选择性可以通过配体的选择来控制。使用DPPE的反应具有间位选择性，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。 [Ir(cod)Cl]_2/DPPE还催化α,ω-二炔与2,5-二氢呋喃环加成得到双环环己二烯衍生物。与2,3-二氢呋喃和正丁基乙烯基醚反应得到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，包括C-O键的断裂。4)研究了[Ir(cod)Cl]_2/P(OPh)_3催化的烯丙胺化的立体化学。 (R)-1-苯基-2-丙烯基碳酸酯与苄胺反应得到(R)-烯丙胺。发现反应在保留立体化学的情况下进行。较少的