The development of a platinum‐catalyzed desaturation of cyclic ketones to their conjugated α,β‐unsaturated counterparts is reported in this full article. A unique diene‐platinum complex was identified to be an efficient catalyst, which enables direct metal‐enolate formation. The reaction operates under mild conditions without using strong bases or acids. Good to excellent yields can be achieved for diverse and complex scaffolds. A wide range of functional groups, including those sensitive to acids, bases/nucleophiles, or palladium species, are tolerated, which represents a distinct feature from other known desaturation methods. Mechanistically, this platinum catalysis exhibits a fast and reversible α‐deprotonation followed by a rate‐determining β‐hydrogen elimination process, which is different from the prior Pd‐catalyzed desaturation method. Promising preliminary enantioselective desaturation using a chiral‐diene‐platinum complex has also been obtained.

中文翻译：

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铂催化金属甲酸酯直接形成环酮的α，β-去饱和反应

这篇全文报道了铂催化环状酮去饱和为其共轭的α，β-不饱和对应物。独特的二烯铂络合物被认为是一种有效的催化剂，可直接形成金属烯醇盐。该反应在温和条件下进行，无需使用强碱或强酸。对于各种复杂的脚手架，可以实现良好的优良产量。宽泛的官能团，包括对酸，碱/亲核试剂或钯物种敏感的官能团是可以耐受的，这代表了与其他已知的去饱和方法不同的特征。从机理上讲，这种铂催化表现出快速且可逆的α-去质子化，然后是决定速率的β-氢消除过程，这不同于先前的Pd催化的去饱和方法。