(5R,6R)-6-苯基-5-(苯磺酰基乙酰基)二环[2.2.1]-2-庚烯的合成及结构表征

报道了一种制备4-苯基-1-苯磺酰基-3-丁烯-2-酮的新合成方法. 4-苯基-3-丁烯-2-酮与溴化试剂Ph₃P^＋CH₂CH₂- COOHBr 作用, 得到1-溴-4-苯基-3-丁烯-2-酮, 不经分离直接与苯亚磺酸钠发生亲核取代反应, 得到4-苯基-1-苯磺酰基-3-丁烯-2-酮. 将此反应产物作为亲双烯体与环戊二烯在手性钛金属催化剂催化下进行不对称Diels-Alder反应, 得到了＞99% ee 的环加成产物(5R,6R)-6-苯基-5-(苯磺酰基乙酰基)二环2.2.1]-2-庚烯. 用X衍射法对产物的晶体结构进行了测定, 讨论了反应机理, 通过元素分析, NMR, MS对产物的结构进行了表征.

Synthesis and Characterization of (5R,6R)-6-Phenyl-5-(phenylsulfonylacetyl)bicyclo[2.2.1]hept-2-ene

A new method for preparation of 4-phenyl-1-phenylsulfonyl-3-butene-2-one was developed. 1-Bromo-4-phenyl-3-butene-2-one was obtained by the bromination of 4-phenyl-3-butene-2-one with Ph 3P C H2 C H 2COOHBr3-, then reacted with sodium benzene sulfinate directly to give 4-phenyl- 1-phenylsulfonyl-3-butene-2-one in good yield. (5R,6R)-6-Phenyl-5-(phenylsulfonylacetyl)bicyclo2.2.1]- hept-2-ene with>99% ee was obtained by the asymmetric Diels-Alder reaction of 4-phenyl-1-phenyl- sulfonyl-3-butene-2-one with cyclopentadiene catalyzed by chiral titanium reagent. The asymmetric reaction mechanism was discussed and the adduct was characterized by X-ray, IR, MS and NMR spectra.