O'Keefe B Michael, Simmons Nicholas, Martin Stephen F
Department of Chemistry and Biochemistry, The University of Texas at Austin, 1 University Station A5300, Austin, TX 78712-0165.
Tetrahedron. 2011 Jun 17;67(24):4344-4351. doi: 10.1016/j.tet.2011.03.074.
A general and mild protocol for achieving the carbonylative cross-coupling of sterically-hindered, ortho-disubstituted aryl ketones is reported. The commercially available PEPPSI-IPr catalyst is shown to efficiently promote the carbonylative cross-coupling of hindered ortho-disubstituted aryl iodides to give diaryl ketones; traditional phosphine catalysts are less effective. Carbonylative Suzuki-Miyaura cross-couplings provide a diverse array of biaryl ketones in good to excellent yields. The same catalyst is also shown to catalyze a carbonylative Negishi cross-coupling reaction, utilizing a variety of alkynyl zinc reagents to give the corresponding alkynyl aryl ketones. Application of this new methodology to the synthesis of the natural product luteolin is reported.
报道了一种通用且温和的方法，用于实现空间位阻较大的邻二取代芳基酮的羰基化交叉偶联反应。结果表明，市售的PEPPSI-IPr催化剂能够有效地促进受阻邻二取代芳基碘化物的羰基化交叉偶联反应，生成二芳基酮；传统的膦催化剂效果较差。羰基化铃木-宫浦交叉偶联反应能以良好至优异的产率提供多种联芳基酮。同样的催化剂也能催化羰基化根岸交叉偶联反应，利用多种炔基锌试剂生成相应的炔基芳基酮。本文报道了这种新方法在天然产物木犀草素合成中的应用。
