Organic Synthesis based on New Selective Radical Process

1. 基于烷氧基自由基裂解的大环内酯类化合物的新合成。提出了一种基于烷氧基自由基连续均解加成-裂解法合成大环内酯类化合物的新方法。11 - 16元大环内酯，包括(()SY.+-。[)]用这种新方法已有效地制备了-recifeiolide。提出了一种将甾体转化为具有生理活性的18-或19-去甲甾体和环a芳香化甾体的新方法。用该方法合成了几种具有生理活性的18-和19-去甾体。基于新的[2+3]光加成合成杂环醌。设计了一种新的[2+3]型区域选择性光加成2-羟基-1,4-萘醌与多种烯烃wa13EA一步合成2,3-二氢萘醌[2,3-b]呋喃-4,9-二酮。二氢萘呋喃二酮很容易转化为萘[2,3-b]呋喃-4,9-二酮，包括天然醌，成熟醌。以2-氨基醌与各种烯烃的2+3型区域选择性光加成为基础，一步高效合成了2,3-二氢- 1h -苯并[f]吲哚-4,9-二酮ba13EA\：新合成的生理活性异甾体。设计了一种通过5 ~ 6 st13EA\: eps将甾体环酮转化为相同环尺寸的甾体环胺、环硫化物、环碲化物和环硒化物的新方法。用这种方法合成了许多异甾体。其它结果设计了三角肯胺阳极氧化立体选择性合成2,5-二取代吡咯烷、远程官能化新方法、木烷合成新方法、环化新方法等。

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.