Total synthesis of lissodendoric acid A via stereospecific trapping of a strained cyclic allene
Small rings that contain allenes are unconventional transient compounds that have been known since the 1960s. Despite being discovered around the same time as benzyne and offering a number of synthetically advantageous features, strained cyclic allenes have seen relatively little use in chemical syn...
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| Veröffentlicht in: | Science (American Association for the Advancement of Science) 2023-01, Vol.379 (6629), p.261-265 |
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| container_title | Science (American Association for the Advancement of Science) |
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| creator | Ippoliti, Francesca M Adamson, Nathan J Wonilowicz, Laura G Nasrallah, Daniel J Darzi, Evan R Donaldson, Joyann S Garg, Neil K |
| description | Small rings that contain allenes are unconventional transient compounds that have been known since the 1960s. Despite being discovered around the same time as benzyne and offering a number of synthetically advantageous features, strained cyclic allenes have seen relatively little use in chemical synthesis. We report a concise total synthesis of the manzamine alkaloid lissodendoric acid A, which hinges on the development of a regioselective, diastereoselective, and stereospecific trapping of a fleeting cyclic allene intermediate. This key step swiftly assembles the azadecalin framework of the natural product, allows for a succinct synthetic endgame, and enables a 12-step total synthesis (longest linear sequence; 0.8% overall yield). These studies demonstrate that strained cyclic allenes are versatile building blocks in chemical synthesis. |
| doi_str_mv | 10.1126/science.ade0032 |
| format | Article |
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Despite being discovered around the same time as benzyne and offering a number of synthetically advantageous features, strained cyclic allenes have seen relatively little use in chemical synthesis. We report a concise total synthesis of the manzamine alkaloid lissodendoric acid A, which hinges on the development of a regioselective, diastereoselective, and stereospecific trapping of a fleeting cyclic allene intermediate. This key step swiftly assembles the azadecalin framework of the natural product, allows for a succinct synthetic endgame, and enables a 12-step total synthesis (longest linear sequence; 0.8% overall yield). 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| ispartof | Science (American Association for the Advancement of Science), 2023-01, Vol.379 (6629), p.261-265 |
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| source | American Association for the Advancement of Science |
| subjects | Allene Bonding strength Chemical synthesis Chemists Cycloaddition Diels-Alder reactions Fluorides Intermediates Natural products Reagents |
| title | Total synthesis of lissodendoric acid A via stereospecific trapping of a strained cyclic allene |
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