Mechanistic Insight into the Facilitation of β-Lactam Fragmentation through Metal Assistance

Luis Casarrubios; Miguel A. Esteruelas; Carmen Larramona; Agustí Lledõs; Jaime G. Muntaner; Enrique Oñate; Manuel A. Ortuño; Miguel A. Sierra

doi:10.1002/chem.201503595

Mechanistic Insight into the Facilitation of β-Lactam Fragmentation through Metal Assistance

Luis Casarrubios, Miguel A. Esteruelas, Carmen Larramona, Agustí Lledõs, Jaime G. Muntaner, Enrique Oñate, Manuel A. Ortuño, Miguel A. Sierra

Department of Chemistry

Research output: Contribution to journal › Article › Research › peer-review

19 Citations (Scopus)

Abstract

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. The mechanism of OsH6(PiPr3)2-mediated fragmentation of a 4-(2 pyridyl)-2-azetidinone has been investigated by DFT calculations. The addition of the C4-H bond of the substrate to OsH2(PiPr3)2 allows the active participation of an osmium lone pair in the B-type β-lactam fragmentation process. This new mechanism makes the N1-C4/C2-C3 fragmentation of the lactamic core thermally accessible through a stepwise process.

Original language	English
Pages (from-to)	16781-16785
Journal	Chemistry - A European Journal
Volume	21
Issue number	47
DOIs	https://doi.org/10.1002/chem.201503595
Publication status	Published - 1 Nov 2015

Keywords

azetidinone
density functional calculations
hexahydride
osmium
β-lactam fragmentation

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title = "Mechanistic Insight into the Facilitation of β-Lactam Fragmentation through Metal Assistance",

abstract = "{\textcopyright} 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. The mechanism of OsH6(PiPr3)2-mediated fragmentation of a 4-(2 pyridyl)-2-azetidinone has been investigated by DFT calculations. The addition of the C4-H bond of the substrate to OsH2(PiPr3)2 allows the active participation of an osmium lone pair in the B-type β-lactam fragmentation process. This new mechanism makes the N1-C4/C2-C3 fragmentation of the lactamic core thermally accessible through a stepwise process.",

keywords = "azetidinone, density functional calculations, hexahydride, osmium, β-lactam fragmentation",

author = "Luis Casarrubios and Esteruelas, {Miguel A.} and Carmen Larramona and Agust{\'i} Lled{\~o}s and Muntaner, {Jaime G.} and Enrique O{\~n}ate and Ortu{\~n}o, {Manuel A.} and Sierra, {Miguel A.}",

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language = "English",

volume = "21",

pages = "16781--16785",

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Mechanistic Insight into the Facilitation of β-Lactam Fragmentation through Metal Assistance. / Casarrubios, Luis; Esteruelas, Miguel A.; Larramona, Carmen; Lledõs, Agustí; Muntaner, Jaime G.; Oñate, Enrique; Ortuño, Manuel A.; Sierra, Miguel A.

In: Chemistry - A European Journal, Vol. 21, No. 47, 01.11.2015, p. 16781-16785.

Research output: Contribution to journal › Article › Research › peer-review

TY - JOUR

T1 - Mechanistic Insight into the Facilitation of β-Lactam Fragmentation through Metal Assistance

AU - Casarrubios, Luis

AU - Esteruelas, Miguel A.

AU - Larramona, Carmen

AU - Lledõs, Agustí

AU - Muntaner, Jaime G.

AU - Oñate, Enrique

AU - Ortuño, Manuel A.

AU - Sierra, Miguel A.

PY - 2015/11/1

Y1 - 2015/11/1

N2 - © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. The mechanism of OsH6(PiPr3)2-mediated fragmentation of a 4-(2 pyridyl)-2-azetidinone has been investigated by DFT calculations. The addition of the C4-H bond of the substrate to OsH2(PiPr3)2 allows the active participation of an osmium lone pair in the B-type β-lactam fragmentation process. This new mechanism makes the N1-C4/C2-C3 fragmentation of the lactamic core thermally accessible through a stepwise process.

AB - © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. The mechanism of OsH6(PiPr3)2-mediated fragmentation of a 4-(2 pyridyl)-2-azetidinone has been investigated by DFT calculations. The addition of the C4-H bond of the substrate to OsH2(PiPr3)2 allows the active participation of an osmium lone pair in the B-type β-lactam fragmentation process. This new mechanism makes the N1-C4/C2-C3 fragmentation of the lactamic core thermally accessible through a stepwise process.

KW - azetidinone

KW - density functional calculations

KW - hexahydride

KW - osmium

KW - β-lactam fragmentation

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DO - 10.1002/chem.201503595

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