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.

通过金属铟与3-溴-1-碘丙烯反应，在Pd(0)催化剂存在下，依次与羰基化合物偶联，然后与芳基、烯基或烯丙基卤化物偶联，合成了一种新型烯丙基二铟试剂。方便的一锅法合成直链高烯丙醇。因此，开发了一种基于烯丙基二铟试剂的新级联。由3-溴-1-碘丙烯和4-溴-2-碘丁-2-烯制备的二铟试剂最初与亚胺反应，所得产物然后在Pd(PPh_3)_4存在下用有机卤化物处理乙烯基铟化合物，得到直链N-芳基和N-甲苯磺酰基高烯丙胺。来自 3-溴-1-碘丙烯的二铟在溶剂中的少量水中是稳定的，而来自 4-溴-2-碘丁-2-烯的二铟很容易质子化，得到巴豆林试剂。后者二铟与苯甲醛的反应通过与两分子醛的自发偶联主要产生1, 3-和1, 5-二醇，而前者与一分子羰基化合物反应产生乙烯基铟化合物。

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)。