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Gold-Catalyzed Reactions of 1,5- and 1,6-Enynes with Carbonyl Compounds: Cycloaddition vs. Metathesis

机译:1,5-和1,6-烯炔与羰基化合物的金催化反应:环加成反应与复分解反应

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摘要

1,n-Enynes (n=5–7) undergo skeletal rearrangement in the presence of a variety of electrophilic metals as catalysts,[1] whereas in the presence of hetero- or carbo- ACHTUNGTRENUNGnucleophiles, addition products are formed.[2–7] Carbonyl compounds also act as nucleophiles in intra-[8] and inter-ACHTUNGTRENUNGmolecular reactions of 1,6-enynes.[9] In the latter case, 1,6- enynes 1, unsubstituted at the terminal alkene (R1=R2=H), reacted with aldehydes to give tricyclic compounds 2 (Scheme 1).[9] Products 3 of formal [2+2+2] cycloaddition, related to those formed in the intramolecular reaction,[8] were not obtained in this reaction.
机译:1,n-Enynes(n = 5-7)在多种亲电子金属作为催化剂的情况下进行骨架重排[1],而在杂合或碳-乙酰丙酮酸亲核试剂的存在下,会形成加成产物。[2– 7]羰基化合物在1,6-烯炔的[8]内和ACHTUNGTRENUNG分子间反应中也充当亲核试剂。[9]在后一种情况下,未在末端烯烃上取代的1,6-烯炔1(R1 = R2 = H)与醛反应生成三环化合物2(方案1)。[9]在该反应中未获得与分子内反应中形成的产物[8]有关的正式[2 + 2 + 2]环加成产物3。

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