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

• 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
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540549/
• 关键词: carbonyl-allylation; allyltrihalotin; tin(IV) chloride; tin(IV) iodide; tetrabutylammonium iodide; sodium iodide; nucleophilic addition; diastereoselectivity; カルボニルーアリル化; アリルトリクロロスズ; ホモアリルアルコール; トリクロロスタナート; シン-ジアステレオ選択性

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.

在二氯甲烷中用碘将卤化锡（IV）还原为三卤锡酸盐（II），形成五卤锡酸盐（IV）。三卤锡酸盐（II）与烯丙基氯或烯丙基甲磺酸盐反应生成烯丙基三卤锡，再与醛发生亲核加成反应生成相应的高烯丙醇。将三卤锡酸盐应用于炔丙基三卤代锡和丙二烯基三卤代锡的制备。（1）羰基烯丙基化：以3-氯丙烯或2-丙烯基甲磺酸酯与氯化锡和三种等摩尔量的四丁基碘化铵（TBAI）为原料，合成了2-丙烯基三氯锡。与1-氯-2-丁烯的羰基烯丙基化反应仍以低产率进行。用碘化锡代替氯化锡，减少了TBAI的用量（两个等摩尔量），提高了1-氯-2-丁烯与羰基烯丙基化反应的产率。碘化钠代替TBAI用于1，3-咪唑烷-2-酮。（2）羰基丙二烯化和炔丙基化：羰基丙二烯化和炔丙基化与上述羰基烯丙基化类似地用2-丙炔基氯或甲磺酸酯进行。甲磺酸1-甲基-2-丙炔酯和甲磺酸2-丁炔酯分别与醛反应生成相应的2-甲基-3-丁炔-1-醇和2-甲基-2，3-丁二烯-1-醇。

项目成果

Yoshiro Masuyama: "Carbonyl allenylations and propargylations by 3-chloro-1-propyne or 2-propynyl mesylates with tin(IV) chloride and tetrabutylammonium iodide"Synlett. 11. 1713-1715 (2003)

Yoshiro Masuyama：“通过 3-氯-1-丙炔或 2-丙炔基甲磺酸酯与氯化锡 (IV) 和四丁基碘化铵进行的羰基联烯基化和炔丙基化”Synlett。

Yoshiro Masuyama: "Carbonyl allylations by 3-halopropenes or 2-propenyl mesylate with tin(IV) chloride and tetrabutylammonium iodide"Tetrahedron Letters. 44. 2845-2847 (2003)

Yoshiro Masuyama：“3-卤代丙烯或甲磺酸2-丙烯基与氯化锡(IV)和四丁基碘化铵的羰基烯丙基化”四面体快报。

Yoshiro Masuyama: "Carbonyl allenylations and propargylations by 3-chloro-1-propyne or 2-propynyl mesylates with tin(IV) chloride and tetrabutylammonium iodide"Synlett. 1713-1715 (2003)

Yoshiro Masuyama：“通过 3-氯-1-丙炔或 2-丙炔基甲磺酸酯与氯化锡 (IV) 和四丁基碘化铵进行的羰基联烯基化和炔丙基化”Synlett。

Yoshiro Masuyama: "Carbonyl allylations by 3-halopropenes or 2-propenyl mesylate with tin(IV) chloride and tetrabutylammonium iodide"Tetrahedron Letters. 44・. (2003)

Yoshiro Masuyama：“3-卤代丙烯或甲磺酸2-丙烯基与氯化锡(IV)和四丁基碘化铵的羰基烯丙基化”Tetrahedron Letters 44·。