Expeditious Asymmetric Synthesis of Polypropionates Relying on Sulfur Dioxide-Induced C–C Bond Forming Reactions

For a long time, the organic chemistry of sulfur dioxide (SO<sub>2</sub>) consisted of sulfinates that react with carbon electrophiles to generate sulfones. With alkenes and other unsaturated compounds, SO<sub>2</sub> generates polymeric materials such as polysulfones. More r...

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Autores principales:	Pierre Vogel, José Angel Sordo Gonzalo
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	aldol reactions alkoxyallylic cation intermediates apoptolidin A baconipyrones dolabriferol hetero-Diels–Alder reactions Chemical technology TP1-1185 Chemistry QD1-999
Acceso en línea:	https://doaj.org/article/1e67daf9ff37420e98a822965dd2ef0f
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spelling	oai:doaj.org-article:1e67daf9ff37420e98a822965dd2ef0f2021-11-25T17:05:11ZExpeditious Asymmetric Synthesis of Polypropionates Relying on Sulfur Dioxide-Induced C–C Bond Forming Reactions10.3390/catal111112672073-4344https://doaj.org/article/1e67daf9ff37420e98a822965dd2ef0f2021-10-01T00:00:00Zhttps://www.mdpi.com/2073-4344/11/11/1267https://doaj.org/toc/2073-4344For a long time, the organic chemistry of sulfur dioxide (SO<sub>2</sub>) consisted of sulfinates that react with carbon electrophiles to generate sulfones. With alkenes and other unsaturated compounds, SO<sub>2</sub> generates polymeric materials such as polysulfones. More recently, H-ene, sila-ene and hetero-Diels–Alder reactions of SO<sub>2</sub> have been realized under conditions that avoid polymer formation. Sultines resulting from the hetero-Diels–Alder reactions of conjugated dienes and SO<sub>2</sub> are formed more rapidly than the corresponding more stable sulfolenes resulting from the cheletropic additions. In the presence of a protic or Lewis acid catalyst, the sultines derived from 1-alkoxydienes are ionized into zwitterionic intermediates bearing 1-alkoxyallylic cation moieties which react with electro-rich alkenes such as enol silyl ethers and allylsilanes with high stereoselectivity. (C–C-bond formation through Umpolung induced by SO<sub>2</sub>). This produces silyl sulfinates that react with carbon electrophiles to give sulfones (one-pot four component asymmetric synthesis of sulfones), or with Cl<sub>2</sub>, generating the corresponding sulfonamides that can be reacted in situ with primary and secondary amines (one-pot four component asymmetric synthesis of sulfonamides). Alternatively, Pd-catalyzed desulfinylation generates enantiomerically pure polypropionate stereotriads in one-pot operations. The chirons so obtained are flanked by an ethyl ketone moiety on one side and by a prop-1-en-1-yl carboxylate group on the other. They are ready for two-directional chain elongations, realizing expeditious synthesis of long-chain polypropionates and polyketides. The stereotriads have also been converted into simpler polypropionates such as the cyclohexanone moiety of baconipyrone A and B, Kishi’s stereoheptad unit of rifamycin S, Nicolaou’s C<sub>1</sub>–C<sub>11</sub>-fragment and Koert’s C<sub>16</sub>–C<sub>I</sub> fragment of apoptolidin A. This has also permitted the first total synthesis of (-)-dolabriferol.Pierre VogelJosé Angel Sordo GonzaloMDPI AGarticlealdol reactionsalkoxyallylic cation intermediatesapoptolidin Abaconipyronesdolabriferolhetero-Diels–Alder reactionsChemical technologyTP1-1185ChemistryQD1-999ENCatalysts, Vol 11, Iss 1267, p 1267 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	aldol reactions alkoxyallylic cation intermediates apoptolidin A baconipyrones dolabriferol hetero-Diels–Alder reactions Chemical technology TP1-1185 Chemistry QD1-999
spellingShingle	aldol reactions alkoxyallylic cation intermediates apoptolidin A baconipyrones dolabriferol hetero-Diels–Alder reactions Chemical technology TP1-1185 Chemistry QD1-999 Pierre Vogel José Angel Sordo Gonzalo Expeditious Asymmetric Synthesis of Polypropionates Relying on Sulfur Dioxide-Induced C–C Bond Forming Reactions
description	For a long time, the organic chemistry of sulfur dioxide (SO<sub>2</sub>) consisted of sulfinates that react with carbon electrophiles to generate sulfones. With alkenes and other unsaturated compounds, SO<sub>2</sub> generates polymeric materials such as polysulfones. More recently, H-ene, sila-ene and hetero-Diels–Alder reactions of SO<sub>2</sub> have been realized under conditions that avoid polymer formation. Sultines resulting from the hetero-Diels–Alder reactions of conjugated dienes and SO<sub>2</sub> are formed more rapidly than the corresponding more stable sulfolenes resulting from the cheletropic additions. In the presence of a protic or Lewis acid catalyst, the sultines derived from 1-alkoxydienes are ionized into zwitterionic intermediates bearing 1-alkoxyallylic cation moieties which react with electro-rich alkenes such as enol silyl ethers and allylsilanes with high stereoselectivity. (C–C-bond formation through Umpolung induced by SO<sub>2</sub>). This produces silyl sulfinates that react with carbon electrophiles to give sulfones (one-pot four component asymmetric synthesis of sulfones), or with Cl<sub>2</sub>, generating the corresponding sulfonamides that can be reacted in situ with primary and secondary amines (one-pot four component asymmetric synthesis of sulfonamides). Alternatively, Pd-catalyzed desulfinylation generates enantiomerically pure polypropionate stereotriads in one-pot operations. The chirons so obtained are flanked by an ethyl ketone moiety on one side and by a prop-1-en-1-yl carboxylate group on the other. They are ready for two-directional chain elongations, realizing expeditious synthesis of long-chain polypropionates and polyketides. The stereotriads have also been converted into simpler polypropionates such as the cyclohexanone moiety of baconipyrone A and B, Kishi’s stereoheptad unit of rifamycin S, Nicolaou’s C<sub>1</sub>–C<sub>11</sub>-fragment and Koert’s C<sub>16</sub>–C<sub>I</sub> fragment of apoptolidin A. This has also permitted the first total synthesis of (-)-dolabriferol.
format	article
author	Pierre Vogel José Angel Sordo Gonzalo
author_facet	Pierre Vogel José Angel Sordo Gonzalo
author_sort	Pierre Vogel
title	Expeditious Asymmetric Synthesis of Polypropionates Relying on Sulfur Dioxide-Induced C–C Bond Forming Reactions
title_short	Expeditious Asymmetric Synthesis of Polypropionates Relying on Sulfur Dioxide-Induced C–C Bond Forming Reactions
title_full	Expeditious Asymmetric Synthesis of Polypropionates Relying on Sulfur Dioxide-Induced C–C Bond Forming Reactions
title_fullStr	Expeditious Asymmetric Synthesis of Polypropionates Relying on Sulfur Dioxide-Induced C–C Bond Forming Reactions
title_full_unstemmed	Expeditious Asymmetric Synthesis of Polypropionates Relying on Sulfur Dioxide-Induced C–C Bond Forming Reactions
title_sort	expeditious asymmetric synthesis of polypropionates relying on sulfur dioxide-induced c–c bond forming reactions
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/1e67daf9ff37420e98a822965dd2ef0f
work_keys_str_mv	AT pierrevogel expeditiousasymmetricsynthesisofpolypropionatesrelyingonsulfurdioxideinducedccbondformingreactions AT joseangelsordogonzalo expeditiousasymmetricsynthesisofpolypropionatesrelyingonsulfurdioxideinducedccbondformingreactions
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Expeditious Asymmetric Synthesis of Polypropionates Relying on Sulfur Dioxide-Induced C–C Bond Forming Reactions

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