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

我们已经研究了以下反应。1）[ir（cod）Cl] _2/dppe催化的Allicyl酗酒1,1-二取代-2,3-丁二烯基乙酸乙酸酯乙酸乙烯酸酯为Quaternary CarbonCenterα提供α至Allene的产物。该反应是一种为Allene构建第四纪碳中心α的有效方法。该反应通过1-甲基-3,3-二取代的π-酰基虹膜中间2）1,6-烯烯与monoynes反应，在存在催化量的[ir（cod）cl] _2 _2/配体的情况下给出了环己二烯衍生物。 DPPE最适合环加成。非对映选择环节也是可能的。在没有monoynes的情况下，将1,6-烯烯环异构体为（Z）-1-烷基二烯-2-甲基环戊烷衍生物。 DPPF最适合于环异构化。这些结果是高度z选择性环化组体的第一个例子。3）[ir（cod）cl] _2/dppe是与monoynes一起使用α，ω-二烯元素的新的催化剂，以使多进定的苯衍生物具有高收益率。可以使用内部单型和终端单基。该反应耐受诸如酒精，胺，烯烃，以太，卤素和硝化物等广泛的官能团。 1,6-八核衍生物与1-烷基的反应产生了正常产物和元产品。调节选择性可以通过配体的选择来控制。使用DPPE的反应是元选择性的，元选择性高达82％。使用DPPF的反应是正向选择性的，正常选择性高达88％。我们提出了一种说明这种法规选择性环加成的机制。 [ir（cod）cl] _2/dppe还用2,5-二氢呋喃催化了α，ω-二烯的环加成，以产生双环环己二烯衍生物。与2,3-二氢呋喃和N-丁基乙烯基醚的反应产生了苯衍生物，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香化的机制，其中包括C-O键的裂解。4）[IR（COD）CL] _2/P（OPH）_3-催化的烯丙基事故的立体化学已研究。（R）-1-苯基-2-丙烯基碳酸胺与苄胺的反应给出了（R） - 丙氨酸胺。发现该反应继续保持立体化学的保留。较少的