Preparation of Tri- and Tetrasubstituted Allenes via Regioselective Lateral Metalation of Benzylic (Trimethylsilyl)alkynes Using TMPZnCl center dot LiCl

作者：Quinio Pauline; Francois Cyril; Cuesta Ana Escribano; Steib Andreas K; Achrainer Florian; Zipse Hendrik; Karaghiosoff Konstantin; Knochel Paul^*

来源：Organic Letters, 2015, 17(4): 1010-1013.

DOI：10.1021/acs.orglett.5b00114

The zincation of various 1-(trimethylsilyl)-3-aryl-1-propynes with TMPZnCl center dot LiCl followed by a Pd-catalyzed coupling with aryl halides provides arylated allenes in 5292% yield. Subsequent metalation with TMPZnCl center dot LiCl and cross-coupling with a second different aryl halide provides regioselectively tetrasubstituted allenes in 4270% yield. This sequence can be performed in a one-pot procedure. DFT calculations and NMR studies support the formation of allenylzinc and propargyllithium intermediates starting from 1-(trimethylsilyl)-3-phenyl-1-propyne.

• 出版日期2015-2-20