Development of catalytic reactions via π-allyl iridium intermediate

铱络合物已被用作氢化催化剂。铱络合物催化的碳-碳键形成受到的关注要少得多。首次发现[Ir（cod）Cl]_2/4P（Oph）_3是一种有效的烯丙基烷基化催化剂。该反应经由π-烯丙基铱中间体进行，该中间体通过烯丙基酯与铱络合物的氧化加成形成。π-烯丙基铱中间体的化学性质对有机合成有一定的应用价值。本研究的目的是开发以π-烯丙基铱为中间体的催化反应.我们发现铱配合物是一种有效的烯丙基胺化催化剂。溶剂对催化活性有很大影响。使用极性溶剂如EtOH对于以高产率获得产物是必要的。在[Ir（cod）Cl]_2/4P（Oph）_3催化下，（E）-3-取代-2-丙烯基碳酸酯和1-取代-2-丙烯基碳酸酯与吡咯烷反应，得到了一系列新的化合物 ...更多信息 具有高达99%选择性的支链胺。仲胺和伯胺都可以使用。当使用伯胺时，发生选择性单烯丙基化。没有获得二烯丙基化产物。1，1-二取代-2-丙烯基乙酸酯与胺反应只生成α，α-二取代烯丙基胺。该反应提供了将有机金属试剂加成到酮亚胺上以制备此类胺的替代途径。（N）-3-取代-2-丙烯基碳酸酯与胺反应生成（N）-直链胺，选择性高达100%.在所有情况下，均未获得（E）-直链胺。本文所述的选择性在类似的钯络合物催化反应中没有实现。乙酸烯炔酯的烯丙基烷基化反应研究了乙酸烯炔酯的烯丙基烷基化反应。在催化量的[Ir（cod）Cl]_2和P（Oet）_3（P/Ir = 2）存在下，2-乙烯基-2-庚炔基乙酸酯与钠丙二酸二乙酯反应，以92%的选择性得到支化产物。反应通过1-（1-炔基）-π-烯丙基铱中间体进行。我们在1-（1-炔基）-取代烯丙基末端实现了高度区域选择性的烷基化。少

Iridium complexes have been used as a hydrogenation catalyst. Much less attention has been paid to iridium complex-catalyzed carbon-carbon bond formation. We first showed that [Ir(cod)Cl]_2/4P(Oph)_3 is an efficient catalyst for allylic alkylation. The reaction proceeds via π-allyl iridium intermediate, which is formed by oxidative addition of allylic esters to an iridium complex. The chemistry of π-allyl iridium intermediate should be useful for organic synthesis. The aim of this research project is to develop catalytic reactions via π-allyl iridium intermediate.1. Allylic animationWe found that an iridium complex is an efficient catalyst for allylic animation. The solvent strongly affected the catalytic activity. The use of a polar solvent such as EtOH is essential for obtaining the products in high yield. The reaction of (E)-3-substituted-2-propenyl carbonate and 1-substituted-2-propenyl carbonate with pyrrolidine in the presence of a catalytic amount of [Ir(cod)Cl]_2/4P(Oph)_3 gave … More a branched amine with up to 99 % selectivity. Both secondary and primary amines could be used. When a primary amine was used, selective monoallylation occurred. No diallylation product was obtained. The reaction of 1,1-disubstituted-2-propenyl acetate with amines exclusively gave an α,α-disubstituted allylic amine. This reaction provides an alternative route to the addition of an organometallic reagent to ketimines for preparation of such amines. The reaction of (Ζ)-3-substituted-2-propenyl carbonate with amines gave (Ζ)-linear amines with up to 100 % selectivity. In all cases, no (Ε)-linear amine was obtained. The selectivities described here have not been achieved in similar palladium complex-catalyzed reactions.2. Allylic alkylation of enynyl acetatesWe examined allylic alkylation of enynyl acetates. The reaction of 2-ethenyl-2-heptynyl acetate with diethyl sodiomalonate in the presence of a catalytic amount of [Ir(cod)Cl]_2 and P(Oet)_3 (P/Ir = 2) gave a branched product in 92 % selectivity. The reaction proceeds via 1-(1-alkynyl)-π-allyl iridium intermediate. We achieved a highly regioselective alkylation at 1-(1-alkynyl)-substituted allylic terminus. Less