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Catalytic Asymmetric Spirocyclizing Diels–Alder Reactions of Enones: Stereoselective Total and Formal Syntheses of α-Chamigrene, β-Chamigrene, Laurencenone C, Colletoic Acid, and Omphalic Acid
[Image: see text] We disclose a general catalytic enantioselective Diels–Alder reaction of exo-enones with dienes to give spirocyclanes. The obtained products feature highly congested quaternary stereogenic spirocenters and are used in concise total and formal syntheses of several sesquiterpenes, in...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9026245/ https://www.ncbi.nlm.nih.gov/pubmed/35389217 http://dx.doi.org/10.1021/jacs.2c01971 |
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author | Ghosh, Santanu Erchinger, Johannes Eike Maji, Rajat List, Benjamin |
author_facet | Ghosh, Santanu Erchinger, Johannes Eike Maji, Rajat List, Benjamin |
author_sort | Ghosh, Santanu |
collection | PubMed |
description | [Image: see text] We disclose a general catalytic enantioselective Diels–Alder reaction of exo-enones with dienes to give spirocyclanes. The obtained products feature highly congested quaternary stereogenic spirocenters and are used in concise total and formal syntheses of several sesquiterpenes, including of α-chamigrene, β-chamigrene, laurencenone C, colletoic acid, and omphalic acid. The stereo- and regioselectivities of our spirocyclizing cycloaddition are effectively controlled by strongly acidic and confined imidodiphosphorimidate catalysts. Computational studies shed light on the origin of reactivity and selectivity. |
format | Online Article Text |
id | pubmed-9026245 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-90262452022-04-25 Catalytic Asymmetric Spirocyclizing Diels–Alder Reactions of Enones: Stereoselective Total and Formal Syntheses of α-Chamigrene, β-Chamigrene, Laurencenone C, Colletoic Acid, and Omphalic Acid Ghosh, Santanu Erchinger, Johannes Eike Maji, Rajat List, Benjamin J Am Chem Soc [Image: see text] We disclose a general catalytic enantioselective Diels–Alder reaction of exo-enones with dienes to give spirocyclanes. The obtained products feature highly congested quaternary stereogenic spirocenters and are used in concise total and formal syntheses of several sesquiterpenes, including of α-chamigrene, β-chamigrene, laurencenone C, colletoic acid, and omphalic acid. The stereo- and regioselectivities of our spirocyclizing cycloaddition are effectively controlled by strongly acidic and confined imidodiphosphorimidate catalysts. Computational studies shed light on the origin of reactivity and selectivity. American Chemical Society 2022-04-07 2022-04-20 /pmc/articles/PMC9026245/ /pubmed/35389217 http://dx.doi.org/10.1021/jacs.2c01971 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Ghosh, Santanu Erchinger, Johannes Eike Maji, Rajat List, Benjamin Catalytic Asymmetric Spirocyclizing Diels–Alder Reactions of Enones: Stereoselective Total and Formal Syntheses of α-Chamigrene, β-Chamigrene, Laurencenone C, Colletoic Acid, and Omphalic Acid |
title | Catalytic
Asymmetric Spirocyclizing Diels–Alder
Reactions of Enones: Stereoselective Total and Formal Syntheses of
α-Chamigrene, β-Chamigrene, Laurencenone
C, Colletoic Acid, and Omphalic Acid |
title_full | Catalytic
Asymmetric Spirocyclizing Diels–Alder
Reactions of Enones: Stereoselective Total and Formal Syntheses of
α-Chamigrene, β-Chamigrene, Laurencenone
C, Colletoic Acid, and Omphalic Acid |
title_fullStr | Catalytic
Asymmetric Spirocyclizing Diels–Alder
Reactions of Enones: Stereoselective Total and Formal Syntheses of
α-Chamigrene, β-Chamigrene, Laurencenone
C, Colletoic Acid, and Omphalic Acid |
title_full_unstemmed | Catalytic
Asymmetric Spirocyclizing Diels–Alder
Reactions of Enones: Stereoselective Total and Formal Syntheses of
α-Chamigrene, β-Chamigrene, Laurencenone
C, Colletoic Acid, and Omphalic Acid |
title_short | Catalytic
Asymmetric Spirocyclizing Diels–Alder
Reactions of Enones: Stereoselective Total and Formal Syntheses of
α-Chamigrene, β-Chamigrene, Laurencenone
C, Colletoic Acid, and Omphalic Acid |
title_sort | catalytic
asymmetric spirocyclizing diels–alder
reactions of enones: stereoselective total and formal syntheses of
α-chamigrene, β-chamigrene, laurencenone
c, colletoic acid, and omphalic acid |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9026245/ https://www.ncbi.nlm.nih.gov/pubmed/35389217 http://dx.doi.org/10.1021/jacs.2c01971 |
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