1,5-Hydrogen Atom Transfer/Surzur–Tanner Rearrangement: A Radical Cascade Approach for the Synthesis of 1,6-Dioxaspiro[4.5]decane and 6,8-Dioxabicyclo[3.2.1]octane Scaffolds in Carbohydrate Systems
The 1,5-HAT–1,2-(ester)alkyl radical migration (Surzur–Tanner rearrangement) radical/polar sequence triggered by alkoxyl radicals has been studied on a series of C-glycosyl substrates with 3-C-(α,β-d,l-glycopyranosyl)1-propanol and C-(α-d,l-glycopyranosyl)methanol structures prepared from chiral pool d- and l-sugar. The use of acetoxy and diphenoxyphosphatoxy as leaving groups provides an efficient construction of 10-deoxy-1,6-dioxaspiro[4.5]decane and 4-deoxy-6,8-dioxabicyclo[3.2.1]octane frameworks. The alkoxyl radicals were generated by the reaction of the corresponding N-alkoxyphthalimides with group 14 hydrides [n-Bu3SnH(D) and (TMS)3SiH], and in comparative terms, the reaction was also initiated by visible light photocatalysis using the Hantzsch ester/fac-Ir(ppy)3 procedure. Special attention was devoted to the influence of the relative stereochemistry of the centers involved in the radical sequence on the reaction outcome. The addition of BF3•Et2O as a catalyst to the radical sequence resulted in a significant increase in the yields of the desired bicyclic ketals.
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American Chemical Society
2021-11-05
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Subjects: | Chemical structure, Hydrogen isotopes, Alcohols, Conformation, Organic compounds, |
Online Access: | http://hdl.handle.net/10261/250968 http://dx.doi.org/10.13039/100012000 http://dx.doi.org/10.13039/501100003329 |
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dig-ipna-es-10261-2509682021-12-09T10:04:07Z 1,5-Hydrogen Atom Transfer/Surzur–Tanner Rearrangement: A Radical Cascade Approach for the Synthesis of 1,6-Dioxaspiro[4.5]decane and 6,8-Dioxabicyclo[3.2.1]octane Scaffolds in Carbohydrate Systems León, Elisa I. Martín, Ángeles Montes, Adrián S. Pérez-Martín, Inés Rodríguez, María del Sol Suárez, Ernesto Ministerio de Economía y Competitividad (España) Fundación CajaCanarias Gobierno de Canarias Chemical structure Hydrogen isotopes Alcohols Conformation Organic compounds The 1,5-HAT–1,2-(ester)alkyl radical migration (Surzur–Tanner rearrangement) radical/polar sequence triggered by alkoxyl radicals has been studied on a series of C-glycosyl substrates with 3-C-(α,β-d,l-glycopyranosyl)1-propanol and C-(α-d,l-glycopyranosyl)methanol structures prepared from chiral pool d- and l-sugar. The use of acetoxy and diphenoxyphosphatoxy as leaving groups provides an efficient construction of 10-deoxy-1,6-dioxaspiro[4.5]decane and 4-deoxy-6,8-dioxabicyclo[3.2.1]octane frameworks. The alkoxyl radicals were generated by the reaction of the corresponding N-alkoxyphthalimides with group 14 hydrides [n-Bu3SnH(D) and (TMS)3SiH], and in comparative terms, the reaction was also initiated by visible light photocatalysis using the Hantzsch ester/fac-Ir(ppy)3 procedure. Special attention was devoted to the influence of the relative stereochemistry of the centers involved in the radical sequence on the reaction outcome. The addition of BF3•Et2O as a catalyst to the radical sequence resulted in a significant increase in the yields of the desired bicyclic ketals. The authors gratefully acknowledge the financial support from the Investigation Programs of the Ministerio de Economia y Competitividad (CTQ2010-18244), Fundación CajaCanarias (2015-BIO08), and the Gobierno de Canarias (ProID2017010017). A.S.M. is grateful to the CSIC JAE Predoc Program. Peer reviewed 2021-09-27T09:36:40Z 2021-09-27T09:36:40Z 2021-11-05 artículo http://purl.org/coar/resource_type/c_6501 Journal of Organic Chemistry 86(21): 14508–14552 (2021) 0022-3263 http://hdl.handle.net/10261/250968 10.1021/acs.joc.1c01376 1520-6904 http://dx.doi.org/10.13039/100012000 http://dx.doi.org/10.13039/501100003329 en #PLACEHOLDER_PARENT_METADATA_VALUE# MINECO/CTQ2010/18244 Publisher's version https://doi.org/10.1021/acs.joc.1c01376 Sí open American Chemical Society |
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Chemical structure Hydrogen isotopes Alcohols Conformation Organic compounds Chemical structure Hydrogen isotopes Alcohols Conformation Organic compounds |
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Chemical structure Hydrogen isotopes Alcohols Conformation Organic compounds Chemical structure Hydrogen isotopes Alcohols Conformation Organic compounds León, Elisa I. Martín, Ángeles Montes, Adrián S. Pérez-Martín, Inés Rodríguez, María del Sol Suárez, Ernesto 1,5-Hydrogen Atom Transfer/Surzur–Tanner Rearrangement: A Radical Cascade Approach for the Synthesis of 1,6-Dioxaspiro[4.5]decane and 6,8-Dioxabicyclo[3.2.1]octane Scaffolds in Carbohydrate Systems |
description |
The 1,5-HAT–1,2-(ester)alkyl radical migration (Surzur–Tanner rearrangement) radical/polar sequence triggered by alkoxyl radicals has been studied on a series of C-glycosyl substrates with 3-C-(α,β-d,l-glycopyranosyl)1-propanol and C-(α-d,l-glycopyranosyl)methanol structures prepared from chiral pool d- and l-sugar. The use of acetoxy and diphenoxyphosphatoxy as leaving groups provides an efficient construction of 10-deoxy-1,6-dioxaspiro[4.5]decane and 4-deoxy-6,8-dioxabicyclo[3.2.1]octane frameworks. The alkoxyl radicals were generated by the reaction of the corresponding N-alkoxyphthalimides with group 14 hydrides [n-Bu3SnH(D) and (TMS)3SiH], and in comparative terms, the reaction was also initiated by visible light photocatalysis using the Hantzsch ester/fac-Ir(ppy)3 procedure. Special attention was devoted to the influence of the relative stereochemistry of the centers involved in the radical sequence on the reaction outcome. The addition of BF3•Et2O as a catalyst to the radical sequence resulted in a significant increase in the yields of the desired bicyclic ketals. |
author2 |
Ministerio de Economía y Competitividad (España) |
author_facet |
Ministerio de Economía y Competitividad (España) León, Elisa I. Martín, Ángeles Montes, Adrián S. Pérez-Martín, Inés Rodríguez, María del Sol Suárez, Ernesto |
format |
artículo |
topic_facet |
Chemical structure Hydrogen isotopes Alcohols Conformation Organic compounds |
author |
León, Elisa I. Martín, Ángeles Montes, Adrián S. Pérez-Martín, Inés Rodríguez, María del Sol Suárez, Ernesto |
author_sort |
León, Elisa I. |
title |
1,5-Hydrogen Atom Transfer/Surzur–Tanner Rearrangement: A Radical Cascade Approach for the Synthesis of 1,6-Dioxaspiro[4.5]decane and 6,8-Dioxabicyclo[3.2.1]octane Scaffolds in Carbohydrate Systems |
title_short |
1,5-Hydrogen Atom Transfer/Surzur–Tanner Rearrangement: A Radical Cascade Approach for the Synthesis of 1,6-Dioxaspiro[4.5]decane and 6,8-Dioxabicyclo[3.2.1]octane Scaffolds in Carbohydrate Systems |
title_full |
1,5-Hydrogen Atom Transfer/Surzur–Tanner Rearrangement: A Radical Cascade Approach for the Synthesis of 1,6-Dioxaspiro[4.5]decane and 6,8-Dioxabicyclo[3.2.1]octane Scaffolds in Carbohydrate Systems |
title_fullStr |
1,5-Hydrogen Atom Transfer/Surzur–Tanner Rearrangement: A Radical Cascade Approach for the Synthesis of 1,6-Dioxaspiro[4.5]decane and 6,8-Dioxabicyclo[3.2.1]octane Scaffolds in Carbohydrate Systems |
title_full_unstemmed |
1,5-Hydrogen Atom Transfer/Surzur–Tanner Rearrangement: A Radical Cascade Approach for the Synthesis of 1,6-Dioxaspiro[4.5]decane and 6,8-Dioxabicyclo[3.2.1]octane Scaffolds in Carbohydrate Systems |
title_sort |
1,5-hydrogen atom transfer/surzur–tanner rearrangement: a radical cascade approach for the synthesis of 1,6-dioxaspiro[4.5]decane and 6,8-dioxabicyclo[3.2.1]octane scaffolds in carbohydrate systems |
publisher |
American Chemical Society |
publishDate |
2021-11-05 |
url |
http://hdl.handle.net/10261/250968 http://dx.doi.org/10.13039/100012000 http://dx.doi.org/10.13039/501100003329 |
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