α-取代烯酮的溶剂控制分子内[2 + 2]光环加成反应
Solvent-controlled intramolecular [2 + 2] photocycloadditions of alpha-substituted enones.
作者信息
Ng Stephanie M, Bader Scott J, Snapper Marc L
机构信息
Department of Chemistry, Merkert Chemistry Center, Boston College, 2609 Beacon Street, Chestnut Hill, Massachusetts 02467, USA.
出版信息
J Am Chem Soc. 2006 Jun 7;128(22):7315-9. doi: 10.1021/ja060968g.
Abstract
The regio- and stereoselectivity of intramolecular [2 + 2] photocycloadditions of 2'-hydroxyenones are shown to be solvent-dependent. In the presence of aprotic solvents, 2'-hydroxyenones undergo photocycloadditions in a manner consistent with the presence of an intramolecular hydrogen bond between the carbonyl group and the tether's hydroxy functionality. In protic solvents, intermolecular interactions appear to disrupt the intramolecular hydrogen bond, providing products with complementary diastereoselectivity. If the facial accessibility of the alpha-tethered olefin is limited, the cycloadditions proceed to give head-to-tail or head-to-head regioisomers, depending on the nature of the solvent employed.
摘要
2'-羟基烯酮分子内[2 + 2]光环加成反应的区域选择性和立体选择性显示出与溶剂有关。在非质子溶剂存在下，2'-羟基烯酮以与羰基和连接链的羟基官能团之间存在分子内氢键相一致的方式进行光环加成反应。在质子溶剂中，分子间相互作用似乎会破坏分子内氢键，从而提供具有互补非对映选择性的产物。如果α-连接烯烃的面式可及性受到限制，则光环加成反应会根据所用溶剂的性质生成头对尾或头对头区域异构体。
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