A novel preparation of allylic tins applying the reduction of tin(IV) chloride with iodide and its application

碘化物还原氯化锡(IV)制备烯丙基锡的新方法及其应用

基本信息

批准号：
14540549
负责人：
MASUYAMA Yoshiro
金额：
$ 2.43万
依托单位：
Sophia University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2003
项目状态：
已结题

项目摘要

Tin(IV) halides were reduced to trihalostannates(II) with iodide in dichloromethane via the formation of pentahalostannates(IV). The trihalostannates(II) reacted with allylic chlorides or allylic mesylates to prepare allyltrihalotins, which caused nucleophilic addition to aldehydes to afford the corresponding homoallylic alcohols. The trihalostannates(II) were applied into the preparation of propargyltrihalotins and allenyltrihalotins. (1)Carbonyl allylation: 2-Propenyltrichlorotin, derived from 3-chioropropene or 2-propenyl mesylate with tin(IV) chloride and three equimolar amount of tetrabutylammonium iodide (TBAI), caused nucleophilic addition to aldehydes to afford the corresponding homoallylic alcohols in high yields. The carbonyl allylation with 1-chloro-2-butene remained in low yields. The use of tin(IV) iodide instead of tin(IV) chloride cut down the amount of TBAI (two equimolar amount) and enhanced the yields of carbonyl allylation with 1-chloro-2-butene. Sodium iodide instead of TBAI was utilized in 1,3-imidazolidin-2-one. (2)Carbonyl allenylation and propargylation: Carbonyl allenylation and propargylation were carried out with 2-propynyl chloride or mesylate similarly to the carbonyl allylation mentioned above. The reaction of 1-methyl-2-propynyl mesylate or 2-butynyl mesylate with aldehydes afforded the corresponding 2-methyl-3-butyn-1 -ols or 2-methyl-2,3-butadien-1-ols respectively.

在二氯甲烷中，卤化锡（IV）被碘化物还原为三卤锡酸盐（II），形成五卤锡酸盐（IV）。三卤锡酸酯(II)与烯丙基氯或烯丙基甲磺酸酯反应制备烯丙基三卤代丁，这引起醛的亲核加成得到相应的高烯丙醇。将三卤锡酸酯(II)应用于炔丙基三卤代烷和丙二烯基三卤代烷的制备。 (1)羰基烯丙基化：2-丙烯基三氯锡，由3-氯丙烯或2-丙烯基甲磺酸酯与氯化锡(IV)和三等摩尔量的四丁基碘化铵(TBAI)反应，与醛发生亲核加成，得到相应的高烯丙醇。产量。用 1-氯-2-丁烯进行的羰基烯丙基化反应的产率仍然很低。使用碘化锡(IV)代替氯化锡(IV)减少了TBAI的量(两等摩尔量)并提高了与1-氯-2-丁烯的羰基烯丙基化的产率。 1,3-咪唑啉-2-酮中使用碘化钠代替 TBAI。 (2)羰基烯丙基化和炔丙基化：与上述羰基烯丙基化类似，用2-丙炔基氯或甲磺酸酯进行羰基烯丙基化和炔丙基化。甲磺酸1-甲基-2-丙炔酯或甲磺酸2-丁炔酯与醛的反应分别得到相应的2-甲基-3-丁炔-1-醇或2-甲基-2,3-丁二烯-1-醇。