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SYNTHETIC DESIGN FOR CONSTRUCTION OF SOME RING SYSTEMS UTILIZING HETERO ATOMS

利用异质原子构建某些环系统的综合设计

基本信息

批准号：
03453093
负责人：
OHNO Masatomi
金额：
$ 4.42万
依托单位：
Nagoya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1991
资助国家：
日本
起止时间：
1991 至 1992
项目状态：
已结题

项目摘要

(1)Ring-formation reaction for [m+n]-membered rings: mpi-components were designed by combination of a silyl enol ether with some conjugated groups. Thus, in the conjugated system with a pyrrole, indole derivatives were obtained by regioselective [4+2]cycloaddition reaction with acetylenic dienophiles. Furthermore, novel type of [4+3]cycloaddition reaction was developed in the conjugated system with a carnonyl group and its analogs; a seven-membered ring could be constructed via the oxyallyl cation intermediate. CF_3-substituted pyrroles were synthesized by means of [3+2]cycloaddition reaction.(2)Ring-derivatization on unique ring systems: For adamantane, the nitrone at its bridged position and the anti-Bredt type olefin at its bridgeheaded position were generated and studied on the addition reactivity. In the latter case, the compounds could be treated around at room temperature because it was substituted with phenyl and ester groups ; this way of stabilization due to an electronic reason is the first example. For squaric acid, carbon-carbon bond formation reaction was carried out under electrophilic conditions using an unsaturated organosilanes, and 1,2-vs 1,4-addition was found to occur depending on the nature of substituents, Lewis acid and reaction temperature. The adducts were further converted to butenolides. For C_<60>, enough addition reactivity of azo-compound as well as some 1,3-dipoles and dienophiles were confirmed in the preliminary works.

（1）[m+n]元环的成环反应：通过烯醇醚与共轭基团的结合，设计了mpi-组分。因此，在含吡咯的共轭体系中，吲哚衍生物与炔属亲双烯体通过区域选择性[4+2]环加成反应得到。此外，在共轭体系中，还发现了一种新的[4+3]环加成反应，即通过烯丙基阳离子中间体，可以形成一个七元环。通过[3+2]环加成反应合成了CF_3取代的吡咯。（2）独特环系上的环衍生化反应：对金刚烷，在桥位上生成了硝酮和反Bredt型烯烃，并研究了加成反应活性。在后一种情况下，化合物可以在室温下处理，因为它被苯基和酯基取代;这种由于电子原因而稳定的方式是第一个例子。对于方酸，使用不饱和有机硅烷在亲电条件下进行碳-碳键形成反应，发现1，2-和1，4-加成的发生取决于取代基的性质、刘易斯酸和反应温度。加合物进一步转化为丁烯内酯。对于C_<60>，初步工作证实了偶氮化合物以及一些1，3-偶极和亲双烯体具有足够的加成反应活性。