Stereoretentive Pd-catalysed Stille cross-coupling reactions of secondary alkyl azastannatranes and

Abstract

The development of transition metal-catalysed cross-coupling reactions has greatly influenced the manner in which the synthesis of complex organic molecules is approached. A wide variety of methods are now available for the formation of C(sp2)–C(sp2) bonds, and more recent work has focused on the use of C(sp3) electrophiles and nucleophiles. The use of secondary and tertiary alkyl nucleophiles in cross-coupling reactions remains a challenge because of the propensity of these alkyl groups to isomerize under the reaction conditions. Here, we report the development of a general Pd-catalysed process for the stereoretentive cross-coupling of secondary alkyl azastannatrane nucleophiles with aryl chlorides, bromides, iodides and triflates. Coupling partners with a wide range of electronic characteristics are well tolerated. The reaction occurs with minimal isomerization of the secondary alkyltin nucleophile, and with retention of absolute configuration. This process constitutes the first general method to use secondary alkyltin reagents in cross-coupling reactions. A general method for the stereoretentive Pd-catalysed cross-coupling of secondary alkyl azastannatranes and aryl electrophiles is described. This work constitutes the first example of a stereoretentive cross-coupling reaction using an unactivated, isolable, optically active organometallic nucleophile.

Cite this article

Li, L., Wang, CY., Huang, R. et al. Stereoretentive Pd-catalysed Stille cross-coupling reactions of secondary alkyl azastannatranes and aryl halides. Nature Chem 5, 607–612 (2013). https://doi.org/10.1038/nchem.1652

View full text

>> Full Text:   Stereoretentive Pd-catalysed Stille cross-coupling reactions of secondary alkyl azastannatranes and