Practical synthetic methodology using a divalent titanium compound

1）以内炔、末端炔和炔丙基溴为原料，合成了苄基钛配合物。该方法允许制备多取代苯衍生物。2）在二价钛试剂的存在下，内部乙炔、末端乙炔和硫腈的反应得到吡啶基钛试剂，从而允许容易地获得吡啶衍生物。3）具有烯炔-、烯二炔-、烯二炔-的π-共轭低聚物，使用1-碘-3-炔-1-烯烃作为结构单元制备杂芳族-烯炔单元。4）1，4-二碘-1，发展了3-链二烯，包括与铜酸盐的区域选择性偶联反应，以及在催化量的Pd催化剂存在下与格氏试剂的区域选择性偶联反应。研究了1-碘-1，3-链二烯与镁络合物的区域选择性镁化反应。

The following new synthetic methods using a divalent titanium complex have been developed1)A facile method for synthesizing benzyltitanium complex from internal acetylenes, terminal acetylenes and propargyl bromides was developed. The method allowed to prepare poly-substituted benzene derivatives.2)The reaction of internal acetylenes, terminal acetylene and sulphonitrile in the presence of the divalent titanium reagent afforded pyridinyl titanium reagents, thus allowing to easy access to pyridine derivatives.3)π-Conjugated oligomers having enyne-, endiyne-, heteroaromatic-enyne units were prepared using a 1-iodo-3-yne-1-alkaene as building block.4)Regio-selective reactions of 1,4-diiodo-1,3-alkadienes were developed which included regio-selective coupling reactions with cuprates, and with Grignard reagents in the presence of a catalytic amount of Pd-catalysis. The regioselective magnesiation of 1-iodo-1,3-alkadienes with a magnesium ate complex was also developed.