[2+1+1] Assembly of spiro beta-lactams by Rh(ii)-catalyzed reaction of diazocarbonyl compounds with azirines/isoxazoles

Результат исследований: Научные публикации в периодических изданияхстатьянаучнаярецензирование

Выдержка

A domino synthesis of dispiro-fused N-vinyl beta-lactams from diazo-Meldrum's acid and 2H-azirines or 5-alkoxyisoxazoles via the "2-azabuta-1,3-diene formation/Staudinger ketene-imine cycloaddition" sequence is described. The Rh-2(Piv)(4)-catalyzed formation of the 2-azabuta-1,3-diene intermediates in the first stage of the reaction sequence proceeds via addition of the rhodium carbenoid to the azirines/isoxazoles and provides the first example of the generation of iminium-type ylides from diazo-Meldrum's acid. This methodology was extended to monospiro-beta-lactams, which were synthesized in two steps using acyclic alpha-diazocarbonyl compounds in the stage of the formation of 2-azabuta-1,3-dienes. The method allows for the rapid assemblage of the carbon part of the azetidin-2-one system from diazo compounds only and affords spiro- and dispiro-beta-lactams in moderate yields. A bromine atom in the 2-bromoalkenyl moiety of the synthesized beta-lactams can be easily substituted by hydrogen under catalytic hydrogenation conditions or by 2-pyridyl-substituent via the Stille cross-coupling reaction.

Язык оригиналаАнглийский
Страницы (с-по)6821-6830
Число страниц10
ЖурналOrganic and Biomolecular Chemistry
Том17
Номер выпуска28
DOI
СостояниеОпубликовано - 28 июл 2019

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@article{29dce4cc851a4d7aa95c23b71585d2ac,
title = "[2+1+1] Assembly of spiro beta-lactams by Rh(ii)-catalyzed reaction of diazocarbonyl compounds with azirines/isoxazoles",
abstract = "A domino synthesis of dispiro-fused N-vinyl beta-lactams from diazo-Meldrum's acid and 2H-azirines or 5-alkoxyisoxazoles via the {"}2-azabuta-1,3-diene formation/Staudinger ketene-imine cycloaddition{"} sequence is described. The Rh-2(Piv)(4)-catalyzed formation of the 2-azabuta-1,3-diene intermediates in the first stage of the reaction sequence proceeds via addition of the rhodium carbenoid to the azirines/isoxazoles and provides the first example of the generation of iminium-type ylides from diazo-Meldrum's acid. This methodology was extended to monospiro-beta-lactams, which were synthesized in two steps using acyclic alpha-diazocarbonyl compounds in the stage of the formation of 2-azabuta-1,3-dienes. The method allows for the rapid assemblage of the carbon part of the azetidin-2-one system from diazo compounds only and affords spiro- and dispiro-beta-lactams in moderate yields. A bromine atom in the 2-bromoalkenyl moiety of the synthesized beta-lactams can be easily substituted by hydrogen under catalytic hydrogenation conditions or by 2-pyridyl-substituent via the Stille cross-coupling reaction.",
keywords = "CARBENOID FUNCTIONALIZATION, RHODIUM CARBENOIDS, CYCLOADDITION REACTION, DIAZO-COMPOUNDS, KETENES, IMINES, ESTERS, DIAZOKETONES, INSERTION, COPPER",
author = "Golubev, {Artem A.} and Smetanin, {Ilia A.} and Anastasiya Agafonova and Nikolai Rostovskii and Khlebnikov, {Alexander F.} and Starova, {Galina L.} and Novikov, {Mikhail S.}",
year = "2019",
month = "7",
day = "28",
doi = "10.1039/c9ob01301f",
language = "Английский",
volume = "17",
pages = "6821--6830",
journal = "Organic and Biomolecular Chemistry",
issn = "1477-0520",
publisher = "Royal Society of Chemistry",
number = "28",

}

[2+1+1] Assembly of spiro beta-lactams by Rh(ii)-catalyzed reaction of diazocarbonyl compounds with azirines/isoxazoles. / Golubev, Artem A.; Smetanin, Ilia A.; Agafonova, Anastasiya; Rostovskii, Nikolai; Khlebnikov, Alexander F.; Starova, Galina L.; Novikov, Mikhail S.

В: Organic and Biomolecular Chemistry, Том 17, № 28, 28.07.2019, стр. 6821-6830.

Результат исследований: Научные публикации в периодических изданияхстатьянаучнаярецензирование

TY - JOUR

T1 - [2+1+1] Assembly of spiro beta-lactams by Rh(ii)-catalyzed reaction of diazocarbonyl compounds with azirines/isoxazoles

AU - Golubev, Artem A.

AU - Smetanin, Ilia A.

AU - Agafonova, Anastasiya

AU - Rostovskii, Nikolai

AU - Khlebnikov, Alexander F.

AU - Starova, Galina L.

AU - Novikov, Mikhail S.

PY - 2019/7/28

Y1 - 2019/7/28

N2 - A domino synthesis of dispiro-fused N-vinyl beta-lactams from diazo-Meldrum's acid and 2H-azirines or 5-alkoxyisoxazoles via the "2-azabuta-1,3-diene formation/Staudinger ketene-imine cycloaddition" sequence is described. The Rh-2(Piv)(4)-catalyzed formation of the 2-azabuta-1,3-diene intermediates in the first stage of the reaction sequence proceeds via addition of the rhodium carbenoid to the azirines/isoxazoles and provides the first example of the generation of iminium-type ylides from diazo-Meldrum's acid. This methodology was extended to monospiro-beta-lactams, which were synthesized in two steps using acyclic alpha-diazocarbonyl compounds in the stage of the formation of 2-azabuta-1,3-dienes. The method allows for the rapid assemblage of the carbon part of the azetidin-2-one system from diazo compounds only and affords spiro- and dispiro-beta-lactams in moderate yields. A bromine atom in the 2-bromoalkenyl moiety of the synthesized beta-lactams can be easily substituted by hydrogen under catalytic hydrogenation conditions or by 2-pyridyl-substituent via the Stille cross-coupling reaction.

AB - A domino synthesis of dispiro-fused N-vinyl beta-lactams from diazo-Meldrum's acid and 2H-azirines or 5-alkoxyisoxazoles via the "2-azabuta-1,3-diene formation/Staudinger ketene-imine cycloaddition" sequence is described. The Rh-2(Piv)(4)-catalyzed formation of the 2-azabuta-1,3-diene intermediates in the first stage of the reaction sequence proceeds via addition of the rhodium carbenoid to the azirines/isoxazoles and provides the first example of the generation of iminium-type ylides from diazo-Meldrum's acid. This methodology was extended to monospiro-beta-lactams, which were synthesized in two steps using acyclic alpha-diazocarbonyl compounds in the stage of the formation of 2-azabuta-1,3-dienes. The method allows for the rapid assemblage of the carbon part of the azetidin-2-one system from diazo compounds only and affords spiro- and dispiro-beta-lactams in moderate yields. A bromine atom in the 2-bromoalkenyl moiety of the synthesized beta-lactams can be easily substituted by hydrogen under catalytic hydrogenation conditions or by 2-pyridyl-substituent via the Stille cross-coupling reaction.

KW - CARBENOID FUNCTIONALIZATION

KW - RHODIUM CARBENOIDS

KW - CYCLOADDITION REACTION

KW - DIAZO-COMPOUNDS

KW - KETENES

KW - IMINES

KW - ESTERS

KW - DIAZOKETONES

KW - INSERTION

KW - COPPER

U2 - 10.1039/c9ob01301f

DO - 10.1039/c9ob01301f

M3 - статья

VL - 17

SP - 6821

EP - 6830

JO - Organic and Biomolecular Chemistry

JF - Organic and Biomolecular Chemistry

SN - 1477-0520

IS - 28

ER -