Challenges in the Highly Selective [3 + 1]-Cycloaddition of an Enoldiazoacetamide to Form a Donor–Acceptor Cis-Cyclobutenecarboxamide †

A substituted donor–acceptor cyclobutenecarboxamide is synthesized with modest enantiocontrol through a chiral copper(I) complex catalyzed [3 + 1]-cycloaddition reaction of α-acyl diphenylsulfur ylides with 3-siloxy-2-diazo-3-butenamides. With a methyl substituent on the 4-position of the 3-butenami...

Descripción completa

Detalles Bibliográficos
Autores principales: Joyasawal, Sipak, Ma, Donghui, Doyle, Michael P.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2021
Materias:
Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8229219/
https://www.ncbi.nlm.nih.gov/pubmed/34207747
http://dx.doi.org/10.3390/molecules26123520
_version_ 1783712925912924160
author Joyasawal, Sipak
Ma, Donghui
Doyle, Michael P.
author_facet Joyasawal, Sipak
Ma, Donghui
Doyle, Michael P.
author_sort Joyasawal, Sipak
collection PubMed
description A substituted donor–acceptor cyclobutenecarboxamide is synthesized with modest enantiocontrol through a chiral copper(I) complex catalyzed [3 + 1]-cycloaddition reaction of α-acyl diphenylsulfur ylides with 3-siloxy-2-diazo-3-butenamides. With a methyl substituent on the 4-position of the 3-butenamide, the cis-vicinal-3,4-disubstituted cyclobutenecarboxamide is formed with >20:1 diastereocontrol. Donor-acceptor 3-methyl-2-siloxycyclopropenecarboxamide is rapidly formed from the reactant enoldiazoamide and undergoes catalytic ring opening to give only the Z-γ-substituted metallo-enolcarbene. Elimination from 3-siloxy-2-diazo-3-pentenamide to form the conjugated 3-siloxy-2,4-pentadienamide is competitive but minimized at low temperature.
format Online
Article
Text
id pubmed-8229219
institution National Center for Biotechnology Information
language English
publishDate 2021
publisher MDPI
record_format MEDLINE/PubMed
spelling pubmed-82292192021-06-26 Challenges in the Highly Selective [3 + 1]-Cycloaddition of an Enoldiazoacetamide to Form a Donor–Acceptor Cis-Cyclobutenecarboxamide † Joyasawal, Sipak Ma, Donghui Doyle, Michael P. Molecules Article A substituted donor–acceptor cyclobutenecarboxamide is synthesized with modest enantiocontrol through a chiral copper(I) complex catalyzed [3 + 1]-cycloaddition reaction of α-acyl diphenylsulfur ylides with 3-siloxy-2-diazo-3-butenamides. With a methyl substituent on the 4-position of the 3-butenamide, the cis-vicinal-3,4-disubstituted cyclobutenecarboxamide is formed with >20:1 diastereocontrol. Donor-acceptor 3-methyl-2-siloxycyclopropenecarboxamide is rapidly formed from the reactant enoldiazoamide and undergoes catalytic ring opening to give only the Z-γ-substituted metallo-enolcarbene. Elimination from 3-siloxy-2-diazo-3-pentenamide to form the conjugated 3-siloxy-2,4-pentadienamide is competitive but minimized at low temperature. MDPI 2021-06-09 /pmc/articles/PMC8229219/ /pubmed/34207747 http://dx.doi.org/10.3390/molecules26123520 Text en © 2021 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Joyasawal, Sipak
Ma, Donghui
Doyle, Michael P.
Challenges in the Highly Selective [3 + 1]-Cycloaddition of an Enoldiazoacetamide to Form a Donor–Acceptor Cis-Cyclobutenecarboxamide †
title Challenges in the Highly Selective [3 + 1]-Cycloaddition of an Enoldiazoacetamide to Form a Donor–Acceptor Cis-Cyclobutenecarboxamide †
title_full Challenges in the Highly Selective [3 + 1]-Cycloaddition of an Enoldiazoacetamide to Form a Donor–Acceptor Cis-Cyclobutenecarboxamide †
title_fullStr Challenges in the Highly Selective [3 + 1]-Cycloaddition of an Enoldiazoacetamide to Form a Donor–Acceptor Cis-Cyclobutenecarboxamide †
title_full_unstemmed Challenges in the Highly Selective [3 + 1]-Cycloaddition of an Enoldiazoacetamide to Form a Donor–Acceptor Cis-Cyclobutenecarboxamide †
title_short Challenges in the Highly Selective [3 + 1]-Cycloaddition of an Enoldiazoacetamide to Form a Donor–Acceptor Cis-Cyclobutenecarboxamide †
title_sort challenges in the highly selective [3 + 1]-cycloaddition of an enoldiazoacetamide to form a donor–acceptor cis-cyclobutenecarboxamide †
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8229219/
https://www.ncbi.nlm.nih.gov/pubmed/34207747
http://dx.doi.org/10.3390/molecules26123520
work_keys_str_mv AT joyasawalsipak challengesinthehighlyselective31cycloadditionofanenoldiazoacetamidetoformadonoracceptorciscyclobutenecarboxamide
AT madonghui challengesinthehighlyselective31cycloadditionofanenoldiazoacetamidetoformadonoracceptorciscyclobutenecarboxamide
AT doylemichaelp challengesinthehighlyselective31cycloadditionofanenoldiazoacetamidetoformadonoracceptorciscyclobutenecarboxamide

Ejemplares similares