New Radical Reactions by Means of Trialleylmanganate

三烯基锰酸盐的新自由基反应

• 批准号: 09450341
• 负责人: OSHIMA Koichiro
• 金额: $ 9.02万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09450341/
• 关键词: manganese ate complex; Ringle electron transfer; radical cydigation; dibromo compound; α-iodo acetal; actioe manganese; gem-ジブロモアルカン; アリル化; 低原子価金属; グリニャ-ル反応剤; 1,3-ジハロプロペン

1. Radical cyclization of ally1 2-iodopheny1 ether, N, N-dially1-2-iodoaniline by means of trialkylmanganate (II)Treatment of 2-iodophenyl prenyl ether with tributylmanganate, generated from MnClィイD22ィエD2 and three molar amounts of butylithium, in THF afforded 3-isopropenyl-2, 3-dihydrobenzofuran in 88% yield. The reaction proceeds as follows. Single electron transfer from tributylmanganate to 2-iodophenol derivative would give an anion radical which generate phenyl radical under departure of the iodide anion. Exo-mode radical cyclization should afford tertiary carbon radical which recombines with n-BuMn to give the dialkylmanganese compound. Dehydromanganation would provide the final product.2. Reaction of gem-dibromo compounds with trialkylmanganateDialkylation of gem-dibromocyclopropanes with trialkylmanganate was achieved. The reaction was initiated by bromine-manganese exchange. Then alkyl group would migrate from manganese to adjacent carbon under bromide elimination. The second alkylation by RX could provide the dialkylation products. The reaction was successfully applied to the preparation of alkenylsilanes starting from dibromomethyltrialkylsilanes.3. Triallylmanganate-mediated cyclization of diyne, enyne, and diene.Treatment of diyne with triallylmanganate provided bicyclized products containing a seven-membered ring. N,N-Bis (2-nonynyl) benzylamine gave a mixture of 9-benzyl-2, 6-dihexyl-9-azabicyclo [5. 3. 0] deca-1 (7), 2-diene, and 9-benzyl-2, 6-dihexyl-9-azabicyclo [5. 3. 0]-deca-1 (7), 3-diene, upon treatment with triallylmanganate.

1.用三烷基锰酸对烯丙基1-2-碘苯基醚、N,N-二烯丙基1-2-碘苯胺进行自由基环化(II)用由MnClィイD22ィエD2和三摩尔量的丁基锂生成的三丁基锰酸盐在THF中处理2-碘苯基异戊二烯基醚，得到3-异丙烯基-2， 3-二氢苯并呋喃，产率88%。反应如下进行。从锰酸三丁酯到2-碘苯酚衍生物的单电子转移会产生阴离子自由基，该阴离子自由基在碘化物阴离子离开的情况下产生苯基自由基。外型自由基环化应提供叔碳自由基，其与n-BuMn重新结合以得到二烷基锰化合物。脱氢锰即得最终产品。2．偕二溴化合物与三烷基锰酸酯的反应实现了偕二溴环丙烷与三烷基锰酸酯的二烷基化。该反应通过溴-锰交换引发。然后在溴化物消除下烷基会从锰迁移到相邻的碳。通过RX进行第二次烷基化可提供二烷基化产物。该反应成功应用于以二溴甲基三烷基硅烷为原料制备烯基硅烷。 3．三烯丙基锰酸酯介导的二炔、烯炔和二烯的环化。用三烯丙基锰酸酯处理二炔得到含有七元环的双环化产物。 N,N-双(2-壬炔基)苄胺得到9-苄基-2,6-二己基-9-氮杂双环[5。 3. 0]deca-1 (7)、2-二烯和9-苄基-2, 6-二己基-9-氮杂双环[5. 3. 0] 3. 0]-deca-1 (7), 3-二烯，经三烯丙基锰酸盐处理。

项目成果

Rie Inoue, Junko Nakao, Hiroshi Shinokubo, and Koichiro Oshima: "Radical Cyclization of Ally1 2-Iodopheny1 Ether, N, N-Dially1-2-iodoaniline, and-2-Iodoethanal Acetal by Means of Trialkylmanganate(II)."Bull. Chem. Soc. Jpn.. 70. 2039-2049 (1997)

Rie Inoue、Junko Nakao、Hiroshi Shinokubo 和 Koichiro Oshima：“通过三烷基锰酸盐 (II) 实现烯丙基 1-2-碘苯醚、N, N-二烯丙基 1-2-碘苯胺和-2-碘乙缩醛的自由基环化。”公牛。

R.Inoue: "Radical Cyclization of Allyl 2-Iodophenyl Ether,N,N-Diallyl-2-iodoaniline,and 2-Iodoethanal Acetal by Means of Trialkylmanganate (II)" Bull.Chem.Soc.Jpn.,. 70(9). 2039-2049 (1997)

R.Inoue：“烯丙基 2-碘苯基醚、N,N-二烯丙基-2-碘苯胺和 2-碘乙醛缩醛通过三烷基锰酸酯 (II) 的自由基环化”Bull.Chem.Soc.Jpn.,。

J.Tang, K.Oshima: "Generation of allylic manganates from Trimethylmanganate and allylic stannanes and their reactions with epoxides"Tetrahedron Lett.,. 38. 9019-9022 (1997)

J.Tang，K.Oshima：“从三甲基锰酸盐和烯丙基锡生成烯丙基锰酸盐及其与环氧化物的反应”Tetrahedron Lett.，。

Jun Tang, Hideki Yorimitsu, Hirotada Kakiya, Rie Inoue, Hiroshi Shinokubo, and Koichiro Oshima: "Generation of Allylic Manganates from Trimethylmanganate and Allylic Stannanes and Their Reactions with Epoxides."Tetrahedron Lett. 38. 9019-9022 (1997)

Jun Tang、Hideki Yorimitsu、Hirotada Kakiya、Rie Inoue、Hiroshi Shinokubo 和 Koichiro Oshima：“从三甲基锰酸盐和烯丙基锡生成烯丙基锰酸盐及其与环氧化物的反应。”四面体快报。

R.Inoue, K.Oshima: "Radical Cyclization of allyl 2-iodophenyl ether, N.N-diallyl-2-iodoaniline, and 2-iodoanilineand 2 iodoethanal acetal by means of trialkylmangan ate(II)"Bull. Chem. Soi. Jpn.,. 70. 2039-2049 (1997)

R.Inoue、K.Oshima：“烯丙基 2-碘苯醚、N.N-二烯丙基-2-碘苯胺、2-碘苯胺和 2 碘乙缩醛通过三烷基锰酸酯 (II) 进行自由基环化”Bull。