Wu Supeng, Jiao Ziqi, Sung Alex T, Faulhaber Abigail B, Schley Nathan D, Schuppe Alexander W
Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235, United States.
J Am Chem Soc. 2025 Jul 2;147(26):22759-22767. doi: 10.1021/jacs.5c04691. Epub 2025 Jun 16.
Here, we report the light-induced decarboxylative ligand-to-metal charge transfer (LMCT) of Cr(III) carboxylate complexes and demonstrate its applicability toward stereoselective Nozaki-Hiyama-Kishi (NHK) allylation reactions. The critical design element of our reaction was identifying a bipyridyl ligand scaffold that enables a single Cr catalyst to facilitate both photolytic dissociation and aldehyde addition. This approach allows for the direct utilization of carboxylic acids and eliminates the need for external redox reagents. The broad utility of this protocol was demonstrated by the preparation of a variety of homoallylic alcohols in good yields and diastereoselectivities as well as the identification of advantageous retrosynthetic disconnections. Extensive studies supported the LMCT mechanism of this transformation, including the characterization of the catalytically active Cr-carboxylate species.
在此，我们报道了羧酸铬(III)配合物的光诱导脱羧配体到金属的电荷转移(LMCT)，并证明了其在立体选择性野崎-桧山-岸(NHK)烯丙基化反应中的适用性。我们反应的关键设计要素是确定一种联吡啶配体支架，它能使单一的Cr催化剂促进光解离和醛加成。这种方法允许直接使用羧酸，并且无需外部氧化还原试剂。通过以良好的产率和非对映选择性制备各种高烯丙醇以及确定有利的逆合成切断，证明了该方案的广泛实用性。广泛的研究支持了这种转化的LMCT机制，包括对催化活性羧酸铬物种的表征。
