2017 Fiscal Year Final Research Report
A challenge to Baldwin's role: Development of the unified methodology for controlling the cyclization mode
| Project/Area Number |
15K07878
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Research Field |
Chemical pharmacy
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| Research Institution | Kobe Pharmaceutical University |
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Principal Investigator |
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| Project Period (FY) |
2015-04-01 – 2018-03-31
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| Keywords | 環化反応 / ヨウ素 / アルキン / イナミド / β-シリル効果 / Baldwin則 / 環化様式 / 配向基 |
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| Outline of Final Research Achievements |
In the iodocyclization, the regioselectivity of nucleophilic position toward alkynes has established as Baldwin’s role. Therefore, the control of the cyclization mode is difficult when both endo- and exo-mode are favored. I have developed the unified methodology for controlling the iodocyclization mode of alkynes by using directing groups.
Amide-substituted alkynes, namely ynamides, were suitable for endo-selective iodocyclizations. In contrast, the iodocyclization of alkynes proceeded in exo mode when silyl groups were used as directing groups. During the course of this project, I serendipitously found that 3-methylene-4-amido-1,2-diazetidine was prepared for the first time via formal [2+2] cycloaddition of an allenamide and an azo compound. This worked as a formal 1,4-dipole precursor toward nucleophilic addition with various silyl nucleophiles.
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| Free Research Field |
有機化学
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