Enantioselective Rhodium-Catalyzed [2+2+2] Cycloaddition of Alkenyl Isocyanates and Terminal Alkynes:  Application to the Total Synthesis of (+)-Lasubine II

The use of TADDOL-based phosphoramidite ligands on rhodium allows for the incorporation of terminal alkynes in the [2+2+2] cycloaddition with alkenyl isocyanates. Terminal aliphatic alkynes provide bicyclic lactams, while the use of aryl alkynes provides complementary access to vinylogous amides. Pr...

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Published in:Journal of the American Chemical Society 2006-09, Vol.128 (38), p.12370-12371
Main Authors: Yu, Robert T, Rovis, Tomislav
Format: Article
Language:English
Subjects:
Alkenes - chemistry
Alkynes - chemistry
Catalysis
Chemistry
Cyclization
Exact sciences and technology
General and physical chemistry
Isocyanates - chemistry
Quinolizines - chemical synthesis
Quinolizines - chemistry
Rhodium - chemistry
Stereoisomerism
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cited_by cdi_FETCH-LOGICAL-a447t-736412ee9c8eb72713917e6ef4160706e9e640e700415a9ad2ca0139955ad7663
cites cdi_FETCH-LOGICAL-a447t-736412ee9c8eb72713917e6ef4160706e9e640e700415a9ad2ca0139955ad7663
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container_title Journal of the American Chemical Society
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creator Yu, Robert T
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description The use of TADDOL-based phosphoramidite ligands on rhodium allows for the incorporation of terminal alkynes in the [2+2+2] cycloaddition with alkenyl isocyanates. Terminal aliphatic alkynes provide bicyclic lactams, while the use of aryl alkynes provides complementary access to vinylogous amides. Product selectivity seems to be governed by a combination of electronics and sterics, with smaller and/or more electron-deficient substituents favoring lactam formation. The use of homologous alkenyl isocyanates leads to an expedient asymmetric total synthesis of the alkaloid lasubine II.
doi_str_mv 10.1021/ja064868m
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source American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)
subjects Alkenes - chemistry
Alkynes - chemistry
Catalysis
Chemistry
Cyclization
Exact sciences and technology
General and physical chemistry
Isocyanates - chemistry
Quinolizines - chemical synthesis
Quinolizines - chemistry
Rhodium - chemistry
Stereoisomerism
title Enantioselective Rhodium-Catalyzed [2+2+2] Cycloaddition of Alkenyl Isocyanates and Terminal Alkynes:  Application to the Total Synthesis of (+)-Lasubine II
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