Reaction of organotitanium species prepared from gem-dihalides and titanocene(II)

新的合成反应的发展利用有机体试剂准备了与钛烯（II）的反应的宝石二水合物（II）物种已经研究过。使用宝石-二氯多氯-Cpy D22-D2 Ti [P（OEt）二氯D23-D23]二氯D22-D2系统的转化，将酮转化为1-氯和1，1-二氯-1-烯烃，和titanocene（II）-推广的宝石二氯多氯多氯少氯少氯由钛ocene制成的四氮基烯烃合成（II）-使用宝石二氯酮推广的碳基化合物的烯烃..。The organotitanium species prepared from gem-dichlorides and Cp D22 y D2Ti[P（OEt）y D23] y D22 y D2 reacted with ketones and carboxylic esters to afford tetrasubstituted olefins and trisubstituted enol ethers in good yields，respectively. 2。1-氯和1，1-二氯-1-烯烃的合成。有机钛物种的反应用酮制成的碳四氯酰氯，在一个好的年份中生产1，1-二氯-1-烯烃。使用氯管来影响1-氯-1-烯烃和1，1-二氯-1-烯烃的类似特征，是在酮需求上偏离固体需求的比率。Titanocene（II）-促进的宝石二氢氧化物循环使其具有终端橄榄素活力..。The bicyclo[n. 1. 0] derivatives were produced by the simple treatment of the gem-dihalides？ing a terminal olefin moiety with性D22 Ti [P（？t）D23]性D22性D2 in good yields。This result suggested that the organotitanium species generated by the reaction of gem-dihalide with Cp D22 y D2Ti[P（？t）y D23] y D22 was different from the one prepared from thioacetal。这一循环化可能通过宝石-甲基化物质进行。

Development of the new synthetic reactions utilizing organotitanium reagents prepared by the reaction of gem-dihalides with titanocene(II) species were studied. The carbonyl olefination using a gem-Dichloride-CpィイD22ィエD2Ti[P(OEt)ィイD23ィエD23]ィイD22ィエD2 System, transformation of ketones into 1-chloro and 1,1-dichloro-1-alkenes, and titanocene(II)-promoted cyclization of gem-dihalides having a terminal olefin moiety were examined and following results were obtained.1. Synthesis of tetrasubstituted olefins by the titanocene(II)-promoted olefination of carbonyl compounds using gem-dichlorides .... The organotitanium species prepared from gem-dichlorides and CpィイD22ィエD2Ti[P(OEt)ィイD23ィエD23]ィイD22ィエD2 reacted with ketones and carboxylic esters to afford tetrasubstituted olefins and trisubstituted enol ethers in good yields, respectively.2. Synthesis of 1-chloro and 1,1-dichloro-1-alkenes .... The reaction of the organotitanium species prepared from carbon tetrachloride with ketones produced the 1,1-dichloro-1-alkenes in good yields. The similar olefination of ketones using chloroform afforded the 1-chloro-1-alkenes and 1,1-dichloro-1-alkenes, the ratio of which refracted the steric demand on the ketones.3. Titanocene(II)-promoted cyclization of gem-dihalides having a terminal olefin moiety .... The bicyclo[n.1.0] derivatives were produced by the simple treatment of the gem-dihalides having a terminal olefin moiety with CpィイD22ィエD2Ti[P(OEt)ィイD23ィエD23]ィイD22ィエD2 in good yields. This result suggested that the organotitanium species generated by the reaction of gem-dihalide with CpィイD22ィエD2Ti[P(OEt)ィイD23ィエD23]ィイD22ィエD2 was different from the one prepared from thioacetal. This cyclization may proceed through gem-dititanium species.