Das Indrajit, Pal Tarun K, Suresh Cheravakkattu G, Pathak Tanmaya
Department of Chemistry, Indian Institute of Technology, Kharagpur 721 302, India.
J Org Chem. 2007 Jul 20;72(15):5523-33. doi: 10.1021/jo062373+. Epub 2007 Jun 20.
This is the first report on the diastereoselective addition of carbon nucleophiles to vinyl sulfone-modified hex-5-enofuranosides. The stereoelectronic properties of the substituents at the C-3 position and their interactions with the incoming carbon nucleophiles control the diastereoselectivity of addition at the C-5 position, favoring the formation of l-ido derivatives as major products in most of the cases studied. This new concept of stereocontrolled carbon-carbon bond formation in vinyl sulfone-modified carbohydrates is general in nature. The novel chirons generated by this diversity-oriented synthetic method have been implemented in the preparation of a wide range of hexofuranosyl C-5 branched-chain sugars, bicyclic derivatives, chirally pure enals, and densely functionalized carbocycles.
这是关于碳亲核试剂对乙烯基砜修饰的己-5-烯呋喃糖苷进行非对映选择性加成的首篇报道。C-3位取代基的立体电子性质及其与进攻性碳亲核试剂的相互作用控制了C-5位加成的非对映选择性，在大多数研究案例中有利于形成l-ido衍生物作为主要产物。乙烯基砜修饰的碳水化合物中这种立体控制碳-碳键形成的新概念本质上具有普遍性。通过这种多样化导向合成方法产生的新型手性合成子已用于制备多种己呋喃糖基C-5支链糖、双环衍生物、手性纯烯醛和高度官能化的碳环化合物。
