Department of Chemistry, and FQRNT Centre for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke St. W., Montreal, Quebec, H3A 0B8, Canada.
Angew Chem Int Ed Engl. 2023 May 8;62(20):e202301730. doi: 10.1002/anie.202301730. Epub 2023 Apr 12.
A novel method for the formation of Csp -P bonds via the nickel-catalyzed cross-coupling of Umpolung carbonyls and phosphine chlorides is reported herein. This process leads to a series of alkylphosphines, which are characterized as sulfides or borane-phosphine complexes after undergoing further transformation with moderate to good yields. Invaluable free alkylphosphines can be easily obtained by desulfurization or deboration of the products. A possible mechanistic pathway is also discussed. This report represents the first example of using renewable carbonyls as latent organometallic reagent surrogates for cross-coupling with heteroatom electrophiles.
本文报道了一种通过镍催化的羰基化合物与膦氯化物的反转交叉偶联形成 Csp -P 键的新方法。该过程得到一系列的烷基膦，它们在经过进一步的转化后，以中等至良好的收率转化为硫化物或硼烷-膦配合物。通过对产物进行脱硫或脱硼，可以很容易地得到有价值的游离烷基膦。还讨论了一种可能的反应机理。本报告代表了使用可再生羰基化合物作为潜在的有机金属试剂替代物与杂原子亲电试剂进行交叉偶联的首例实例。
