Asymmetric Pd-catalyzed Tsuji-Trost-type allylation is an important catalytic reaction toward chiral natural and unnatural product syntheses. We successfully modified a desalt-type reaction using allyl ester or halide to a dehydrative one using allylic alcohol via the establishment of two redox-mediated donor acceptor bifunctional catalyst systems. These systems were cationic CpRu-Cl-Napy-PyCOOH and cationic CpRu-Naph-diPIM-dioxo-iPr/p-TsOH and were designed on the basis of the soft ruthenium and hard Brønsted acid combined catalyst concept. The complementary use of the two chiral catalysts for dehydrative asymmetric allylation expands the application scope facilitating the utilization of both aliphatic and aromatic allylic alcohols with various nucleophiles in the substrate. In this account, the design, synthesis, and application of these catalysts were reported.

中文翻译：

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使用软钌和硬布朗斯台德酸组合催化剂的不对称脱水烯丙基化

不对称 Pd 催化的 Tsuji-Trost 型烯丙基化是手性天然和非天然产物合成的重要催化反应。我们通过建立两种氧化还原介导的供体受体双功能催化剂系统，成功地将使用烯丙酯或卤化物的脱盐型反应改造成使用烯丙醇的脱水反应。这些系统是阳离子 CpRu-Cl-Napy-PyCOOH 和阳离子 CpRu-Naph-diPIM-dioxo- i Pr/ p-TsOH，是基于软钌和硬布朗斯台德酸组合催化剂概念设计的。两种手性催化剂的互补用于脱水不对称烯丙基化扩大了应用范围，促进了底物中具有各种亲核试剂的脂肪族和芳香族烯丙醇的利用。在这个帐户中，报告了这些催化剂的设计、合成和应用。