2006 Fiscal Year Final Research Report Summary
Development of new synthetic methods utilizing reactivity of alkylidenecarbenes
| Project/Area Number |
16590009
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Chemical pharmacy
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| Research Institution | Nagoya City University |
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Principal Investigator |
AOYAMA Toyohiko Nagoya City University, Graduate School of Pharmaceutical Sciences, Professor, 大学院薬学研究科, 教授 (80080191)
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| Project Period (FY) |
2004 – 2006
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| Keywords | trimethylsilyldiazomethane / alkylidenecarbene / indole / indazole / 2-pyridone / 1-oxaazulene / α,β-epoxyester |
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| Research Abstract |
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.
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