首页> 外文期刊>Chemistry: A European journal >Ir-Catalyzed Asymmetric Allylic Substitutions with (Phosphoramidite)Ir Complexes—Resting States, Synthesis, and Characterization of Catalytically Active (p-Allyl)Ir Complexes
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Ir-Catalyzed Asymmetric Allylic Substitutions with (Phosphoramidite)Ir Complexes—Resting States, Synthesis, and Characterization of Catalytically Active (p-Allyl)Ir Complexes

机译:具有(磷酰胺基)Ir配合物的Ir催化的不对称烯丙基取代基—催化活性(对烯丙基)Ir配合物的重整状态,合成和表征

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摘要

Ir-catalyzed allylic substitution allows monosubstituted allylic substrates to be treated with a broad spectrum of C, N, and O nucleophiles to produce branched products 2 with high selectivity (Scheme 1).[1] The best Ir catalysts at present are generated by base-induced CH activation from [{Ir- ACHTUNGTRENUNG(cod)Cl}2] (cod=cycloocta-1,5-diene) or [{IrACHTUNGTRENUNG(dbcot)Cl}2] (dbcot=dibenzocyclooctatetraene)[2] and a chiral phosphoramidite. Concerning preparative applicability, the so-called salt-free version has proven particularly reliable; it involves production of the nucleophile from its conjugate acid by reaction with carbonate or alkoxide generated in the substitution step.
机译:Ir催化的烯丙基取代使单取代的烯丙基底物可以用广谱的C,N和O亲核试剂处理,从而以高选择性产生支链产物2(方案1)。[1]目前最好的Ir催化剂是由[{Ir-ACHTUNGTRENUNG(cod)Cl} 2](cod = cycloocta-1,5-diene)或[{IrACHTUNGTRENUNG(dbcot)Cl} 2]( dbcot =二苯并环辛酸酯)[2]和手性亚磷酰胺。关于制备的适用性,已证明所谓的无盐版本特别可靠。它涉及通过与取代步骤中生成的碳酸盐或醇盐反应,从其共轭酸生产亲核试剂。

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