Piñeiro-Suárez Martín, Álvarez-Constantino Andrés M, Fañanás-Mastral Martín
Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS), Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain.
ACS Catal. 2023 Apr 10;13(8):5578-5583. doi: 10.1021/acscatal.3c00536. eCollection 2023 Apr 21.
A catalytic asymmetric reaction between allenes, bis(pinacolato)diboron, and allylic -dichlorides is reported. The method involves the coupling of a catalytically generated allyl copper species with the allylic -dichloride and provides chiral internal 1,5-dienes featuring ()-configured alkenyl boronate and alkenyl chloride units with high levels of chemo-, regio-, enantio-, and diastereoselectivity. The synthetic utility of the products is demonstrated with the synthesis of a range of optically active compounds. DFT calculations reveal key noncovalent substrate-ligand interactions that account for the enantioselectivity outcome and the diastereoselective formation of the ()-alkenyl chloride.
报道了一种联烯、双(频哪醇)二硼和烯丙基二氯化物之间的催化不对称反应。该方法涉及催化生成的烯丙基铜物种与烯丙基二氯化物的偶联，并提供具有( )-构型的烯基硼酸酯和烯基氯单元的手性内型1,5-二烯，具有高水平的化学、区域、对映和非对映选择性。通过一系列光学活性化合物的合成证明了产物的合成效用。密度泛函理论计算揭示了关键的非共价底物-配体相互作用，这些相互作用解释了对映选择性结果和( )-烯基氯的非对映选择性形成。
