Organic Synthesis based on New Selective Radical Process

1.基于烷氧基β-断裂的大环内酯类化合物的新合成方法。本文提出了一种基于连续分子内均裂加成-断烷氧自由基合成大环内酯的简便新方法。11至16元大环内酯，包括（（）SY.+-。通过这种新方法有效地制备了（R）-recifeietin。基于烷氧基自由基的β-断裂将甾体转化为生理活性的18-或19-去甲甾体的新方法设计了将甾体转化为18-和19-去甲甾体以及环A-芳构化甾体的新方法。用此方法合成了几种具有生理活性的18-和19-去甲甾体化合物.基于新的[2+3]光加成反应合成杂环醌类化合物。设计了一种新的2-羟基-1，4-萘醌与多种烯烃的[2+3]型区域选择性光加成反应，一步生成2，3-二氢萘并[2，3-B]呋喃-4，9-二酮。二氢萘并呋喃二酮容易转化为萘并[2，3-B]呋喃-4，9-二酮，包括天然醌，maturinone。基于2-氨基醌与各种烯烃的2+3型区域选择性光加成反应，设计了1H-苯并[f]吲哚-4，9-二酮的高效一步合成2，3-二氢-1H-苯并[f]吲哚-4，9-二酮.具有生理活性的杂甾体化合物的新合成。设计了一种通过5 ~ 6个st 13 EA eps将甾体环酮转化为具有相同环尺寸的甾体环胺、环硫醚、环碲醚和环硒醚的新方法。用此方法合成了一系列杂甾体化合物.其他结果设计了δ-烯胺阳极氧化立体选择性合成2，5-二取代吡咯烷类化合物、远程功能化新方法、合成木脂素的新方法、合成鞣花酸的新方法等。

1. New Synthesis of macrolides based on beta-scission of alkoxyl radicals. A simple new method was devised for the synthesis of macrolides based on a consecutive intramolecular homolytic addition-bata-scission of alkoxyl radicals. 11 to 16-Membered macrocyclic lactones including ((〕SY.+-.〔))-recifeiolide have been efficiently prepared by this new method.2. New method for the transformation of steroids into physiologically-active 18- or 19- norsteroids based on bata-scission of alkoxyl radicals New method for transformation of steroids into 18- and 19-norsteroids and ring-A- aromatized steroids was devised. Several physiologically-active 18-, and 19-norsteroids were synthesized by this method.3. Synthesis of heterocyclic quinones based on a new [2+3] photoaddition. A one-step formation of 2,3-dihydronaphto[2,3-b]furan-4,9-diones by a new [2+3] type regioselective photoaddition of 2-hydroxy-1,4-naphthoquinones with a variety of alkenes wa13EA\ : s devised. The dihydronaphthofurandiones were readily transformed into naphtho[2,3-b]furan-4,9-diones including a natural quinone, maturinone. Efficient one-step synthesis of 2,3-dihydro-1H- benz[f]indole-4,9-diones of 1H-benz[f]indole-4,9-diones ba13EA\ : sed on an unprecedented 2+3 type regioselective photoaddition of 2-aminoquinone with various alkenes was also devised.4. New synthesis of physiologically-active heterosteroids. A new method was devised for transforming steroidal cyclic ketones into steroidal cyclic amines, cyclic sulfies, cyclic tellurides, and cyclic selenides with the same ring size via 5 to 6 st13EA\ : eps. A number of heterosteroids were synthesized by this method.5. Other Results stereoselective synthesis of 2,5-disubstituted pyrrolidines by anodic oxidation of delta-alkenylamines, new method for remote functionalization, new synthesis of lignanes, and new method for the annelatioin etc. were devised.