Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore), Fax: (+65) 6791-1961.
Chemistry. 2014 Jan 13;20(3):713-8. doi: 10.1002/chem.201303685. Epub 2013 Dec 9.
A synthetic method to stereoselectively prepare 4-(cyclohexa-1,3-dienyl)-1,3-dioxolanes in good to excellent yields by gold(I)-catalyzed [2+2+1] cycloaddition of 1,6-diyne carbonates and esters with aldehydes is described. The cascade process involves 1,2-acyloxy migration followed by cyclopropenation and cycloreversion. This leads to an unprecedented [2+2+1] cycloaddition of the resulting alkenylgold carbenoid species, examples of which are extremely rare, with two aldehyde molecules at catalyst loadings as low as 1 mol %. The usefulness of this cycloisomerization chemistry was further demonstrated by the transformation of one example to the corresponding phenol.
一种通过金（I）催化的[2+2+1]环加成反应，立体选择性地制备 4-（环己-1,3-二烯基）-1,3-二恶烷的合成方法被描述。该级联过程涉及 1,2-酰氧基迁移，然后是环丙烯化和环重排。这导致了前所未有的[2+2+1]环加成反应，其中的例子非常罕见，在催化剂负载量低至 1 mol%的情况下，用两个醛分子进行反应。这种环异构化化学的有用性通过将一个例子转化为相应的苯酚得到了进一步证明。
