Development of Environmentally Benign Selective Organic Reactions with Allylpolyindium Reagents

烯丙基聚铟试剂环境友好型选择性有机反应的进展

• 批准号: 12640515
• 负责人: ARAKI Shuki
• 金额: $ 2.37万
• 依托单位: Nagoya Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640515/
• 关键词: Indium; Allylation; Polymetalic species; Dianion; Homoallyl alcohol; Homoallylamine; Stereoselectivity; Regioselectivity

A novel allylic diindium reagents were synthesized by the reaction of indium metal with 3-bromo-1-iodopropene, which successively coupled with carbonyl compounds and then with aryl, alkenyl or allyl halides in the presence of a Pd(0) catalyst to afford a convenient one-pot synthesis of linear homoallylic alcohols. Thus, a new cascade based on the allylic diindium reagent has been developed.The di indium reagents, prepared from 3-bromo-1-iodopropene and 4-bromo-2-iodobut- 2-ene, were initially reacted with imines and the resulting vinylindium compounds were then treated with organic halides in the presence of Pd(PPh_3)_4 to give linear N-aryl and N-tosyl homoallylic amines. The diindium from 3-bromo-1-iodopropene is stable in a small amount of water in solvent, whereas the di indium from 4-bromo-2-iodobut-2-ene is easily protonated to give a crotylindium reagent. The reaction of the latter di indium with benzaldehyde gives mainly the 1, 3- and 1, 5-diols via a spontaneous coupling with two molecules of the aldehyde, in contrast to the former which reacts with one molecule of carbonyl compounds to give the vinylindium compounds.

在Pd(0)催化剂的催化下，金属铟与3-溴-1-碘丙烯反应合成了一种新的烯丙基二铟试剂，该试剂先与3-溴-1-碘丙烯偶联，再与芳基、烯基或烯丙基卤化物反应，实现了一锅法合成直链高烯丙醇。以3-溴-1-碘丙烯和4-溴-2-碘-2-烯为原料制备的双铟试剂首先与亚胺反应，然后在Pd(PPh_3)_4存在下与有机卤化物反应生成N-芳基和N-对甲苯磺基高烯丙基胺。从3-溴-1-碘丙烯得到的二铟在少量水中是稳定的，而从4-溴-2-碘-2-烯得到的二铟很容易质子化而得到试剂。后者与苯甲醛反应，主要生成1，3-和1，5-二醇，主要是通过与两个醛分子的自发偶合生成1，3-和1，5-二醇，而前者是与一个分子的羰基化合物反应生成乙烯基化合物。

项目成果

T.Hirashita, H.Yamamura, M.Kawai, S.Araki: "A New Cascade for the One-pot Synthesis of Linear Homoallylic Alcohols with an Allylic Diindium Reagent"Chemical Communications. 387-388 (2001)

T.Hirashita、H.Yamamura、M.Kawai、S.Araki：“用烯丙基二铟试剂一锅合成线性高烯丙醇的新级联”化学通讯。

T.Hirashita, Y.Hayashi, K.Mitsui, S.Araki: "Allylic-type Diindium Reagents. Reactivity toward Electrophiles and Cascade Coupling Reactions with Imines"Journal of Organic Chemistry. 68(印刷中). (2003)

T. Hirashita、Y. Hayashi、K. Mitsui、S. Araki：“烯丙基型二铟试剂。亲电试剂的反应性和与亚胺的级联偶联反应”有机化学杂志 68（出版中）。

T. Hirashita, H. Yamamura, M. Kawai, S. Araki: "A New Cascade for the One-pot Synthesis of Linear Homoallylic Alcohols with an Allylic Diindium Reagent"Chem. Commun.. 387-388 (2001)

T. Hirashita、H. Yamamura、M. Kawai、S. Araki：“用烯丙基二铟试剂一锅合成线性高烯丙醇的新级联”Chem。

T. Hirashita, Y. Hayashi, K. Mitsui, S. Araki: "Allylic-type Diindum Reagent. Reactivity toward Electrophiles and Cascade Coupling Reactions with Imines"J. Org. Chem.. 68(in press). (2003)

T. Hirashita，Y. Hayashi，K. Mitsui，S. Araki：“烯丙基型二铟试剂。对亲电子试剂的反应性以及与亚胺的级联偶联反应”J。

T.Hirashita 他3名: "A New Cascade for the One-pot Synthesis of Linear Homoallylic Alcohols with an Allylic Diindium Reagent"Chemical Communications. 387-388 (2001)

T.Hirashita 和其他 3 人：“用烯丙基二铟试剂一锅合成线性高烯丙醇的新级联”化学通讯 387-388 (2001)。