Development of new synthetic methods utilizing reactivity of alkylidenecarbenes

利用亚烷基碳烯的反应性开发新的合成方法

• 批准号: 16590009
• 负责人: AOYAMA Toyohiko
• 金额: $ 2.24万
• 依托单位: Nagoya City University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16590009/
• 关键词: trimethylsilyldiazomethane; alkylidenecarbene; indole; indazole; 2-pyridone; 1-oxaazulene; α,β-epoxyester; アリーフプロピオラート; アリールグリオキシレート; 1,2-ジヒドロ-1-オキサアズレン; アルキニルピバロイルアニリン; 2,3-ジ置換インドール; β-シリル-α,β-エポキシエステル; 1-オキサ-1,2-ジヒドロアズレン; アリールプロピオル酸エステル

1. N-Tosyl-o-acylanilines smoothly reacted with lithium salt of trimethylsilyldiazomethane (TMSCHN_2) to give 3-substituted indoles via an alkylidenecarbene intermediate in good yield.2. The copper (II)-catalyzed cross-coupling of 3-trimethylsilylindazoles with arylboronic acids regioselectively gave the corresponding 1-aryl-3-trimethylsilylindazoles in high yields.3. Reaction of TMSCHN_2, acylisocyanates, and N-phenylmalenimide gave bicyclic 2-pyridones in good yields in a one-pot process.4. Aryloxypyruvates reacted with TMSC(Ll)N_2 to give 1,2-dihydro-1-oxaazulene-3-carboxylates via an alkylidenecarbene intermediate in moderate yields.5. o-Acyl-N-pivaloylanilines smoothly reacted with TMSC(Li)N_2 to give o-alkynyl-N-pivaloylanilines via an alkylidenecarbene intermediate in good yield.6. Reaction of N-Tosyl-o-acylanilines with TMSC(Li)N_2, followed by treatment with t-BuLi and then electrophiles gave 2,3-disubstituted N-tosylindoles in a one-pot process.7. Reaction of -αketoesters with magnesium bromide salt of TMSCHN_2 followed by in situ treatment with pivalic acid gave a-substituted β-trimethylsilyl-α,β-epoxyesters in an efficient and cis-selective manner.

1. N-甲苯磺酰基-邻酰基苯胺与三甲基甲硅烷基重氮甲烷的锂盐（TMSCHN_2）顺利反应，通过亚烷基碳烯中间体以良好的收率生成3-取代吲哚。2. 铜（II）催化3-三甲基甲硅烷基吲唑与芳基硼酸区域选择性地给出相应的1-芳基-3-三甲基甲硅烷基吲唑以高产率进行。3．TMSCHN_2、酰基异氰酸酯和N-苯基马来酰亚胺在一锅法中以良好的产率反应得到双环2-吡啶酮。4．芳氧基丙酮酸盐与TMSC(L1)N_2反应得到双环2-吡啶酮。 1,2-二氢-1-恶薁-3-羧酸酯5．邻酰基-N-新戊酰苯胺与TMSC(Li)N_2顺利反应，通过亚烷基卡宾生成邻-炔基-N-新戊酰苯胺，收率良好。6． -酰基苯胺与 TMSC(Li)N_2，然后用 t-BuLi 处理，然后亲电子试剂得到一锅法制备 2,3-二取代的 N-甲苯磺酰吲哚。7. -α 酮酯与 TMSCHN_2 的溴化镁盐反应，然后用新戊酸原位处理，得到 α-取代的 β-三甲基甲硅烷基-α,β-环氧酯。高效且顺式选择性的方式。

项目成果

One-pot, cis-selective synthesis of a-substituted β- trimethylsilyl-α, β-epoxyesters from a-ketoesters and diazo(trimethylsilyl)methyl magnesium bromide

由α-酮酯和重氮(三甲基甲硅烷基)甲基溴化镁一锅顺式选择性合成α-取代的β-三甲基甲硅烷基-α,β-环氧酯

• 发表时间: 2006
• 期刊: Tetrahedron Lett. 47
• 作者: Y.Hari;S.Tsuchida;T.Aoyama
• 通讯作者: T.Aoyama

New synthesis of t-butyl 1,2-dihydro-l-oxaazulene-3- carboxylates using lithium trimethylsilyldiazomethane

使用三甲基甲硅烷基重氮甲烷锂新合成 1,2-二氢-1-恶薁-3-甲酸叔丁酯

• 发表时间: 2005
• 期刊: Heterocycles 65
• 作者: H.Takahashi;H.Mitsuzuka;K.Nishiyama;S.Ikegami;Y.Hari;Shin-ichi Ikeda;伊藤 久央;M.Nakakoshi;Naoyoshi Maezaki;K.Kawahata;Hideyo Takahashi;S.Tsuchida
• 通讯作者: S.Tsuchida

Regioselective Synthesis of 1-Arylindazoles via N-Arylation of 3-Trimethylsilylindazoles

通过 3-三甲基硅烷基吲唑的 N-芳基化区域选择性合成 1-芳基吲唑

• 发表时间: 2005
• 期刊: Tetrahedron Letters vol 46
• 作者: Yoshiyuki Hari;Yoshimichi Shoji;Toyohiko Aoyama
• 通讯作者: Toyohiko Aoyama

One-pot, cis-selective synthesis of α-subsutituted β-trimethylsilyl-α,β-epoxyesters from α-ketoesters and diazo(trimethylsilyl) methyl magnesiurr bromide

由α-酮酯和重氮(三甲基硅基)甲基溴化镁一锅顺式选择性合成α-取代的β-三甲基硅基-α,β-环氧酯

• 发表时间: 2006
• 期刊: Tetrahedron Lett. 47
• 作者: Susumu Tsuchida;Yoshiyuki Had;Toyohiko Aoyama
• 通讯作者: Toyohiko Aoyama

One-pot, cis-selective synthesis of α-substituted β-trimethylsilyl-α,β-epoxy-esters from α-ketoesters and diazo(trimethylsilyl)methyl magnesium bromide

由α-酮酯和重氮(三甲基甲硅烷基)甲基溴化镁一锅顺式选择性合成α-取代的β-三甲基甲硅烷基-α,β-环氧酯

• 发表时间: 2006
• 期刊: Tetrahedron Lett. 47
• 作者: Nakajima;N.;Ubukata;M.;Yoshiyuki Hari;M.Kawahata;Yoshiyuki Hari;H.Makita;Yoshiyuki Hari
• 通讯作者: Yoshiyuki Hari