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

我们研究了下列反应。1)[Ir(cod)Cl]_2/ dpe催化1,1-二取代-2,3-丁二烯乙酸酯烯丙基烷基化反应，得到了以季碳中心α为烯丙烯的高产产物。该反应是构建季碳中心α到烯的有效方法。在[Ir(cod)Cl]_2/配体的催化作用下，通过1-亚甲基-3,3-二取代π-烯丙基铱中间体2)1,6-烯炔与单体反应生成环己二烯衍生物。DPPE最适合于环加成。非对映选择性环加成也是可能的。在没有单体的情况下，1,6-炔环异构化成(Z)-1-烷基烯-2-亚甲基环戊烷衍生物。DPPF最适于环异构化。这些结果是高z选择性环异构化的第一个例子。3)[Ir(cod)Cl]_2/DPPE是α，ω-二炔与单炔环加成得到多取代苯衍生物的新催化剂，收率高。可以使用内单音元，也可以使用端单音元。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-炔反应得到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的反应具有元选择性，元选择性高达82%。DPPF为正选择性反应，正选择性可达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2,5-二氢呋喃的环加成，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。我们还提出了一种机制来解释这种新的芳构化，包括C-O键的裂解。4)研究了[Ir(cod)Cl]_2/P(OPh)_3催化烯丙基胺化反应的立体化学。碳酸(R)-1-苯基-2-丙烯酯与苄胺反应得到(R)-烯丙基胺。发现该反应是在立体化学的保留下进行的。少

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