Li Guotao, Zhang Guozhu, Zhang Liming
Department of Chemistry/216, University of Nevada, Reno, 1664 North Virginia Street, Reno, Nevada 89557, USA.
J Am Chem Soc. 2008 Mar 26;130(12):3740-1. doi: 10.1021/ja800001h. Epub 2008 Mar 1.
Propargylic pivalates with electronically unbiased internal alkynes are selectively transformed into (1Z,3E)-2-pivaloxy-1,3-dienes containing various functionalities. The unusual selectivity of 1,2-acyloxy migration over the structurally preferred 3,3-rearrangement is realized. This reaction is highly stereoselective and offers rapid access to dienes for one-pot intra-/intermolecular Diels-Alder reactions either under thermal conditions or with Lewis acid catalysis.
带有电子中性内炔的炔丙基新戊酸酯被选择性地转化为含有各种官能团的(1Z,3E)-2-新戊氧基-1,3-二烯。实现了1,2-酰氧基迁移相对于结构上更有利的3,3-重排的异常选择性。该反应具有高度的立体选择性，并且无论是在热条件下还是在路易斯酸催化下，都能为一锅法分子内/分子间狄尔斯-阿尔德反应快速提供二烯。
