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

Chemistry (Twin Cities)

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

25 Scopus citations

Abstract

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 (US)
Pages (from-to)	16781-16785
Number of pages	5
Journal	Chemistry - A European Journal
Volume	21
Issue number	47
DOIs	https://doi.org/10.1002/chem.201503595
State	Published - Nov 1 2015

Bibliographical note

Publisher Copyright:
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords

azetidinone
density functional calculations
hexahydride
osmium
β-lactam fragmentation

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10.1002/chem.201503595

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

abstract = "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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doi = "10.1002/chem.201503595",

language = "English (US)",

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publisher = "John Wiley and Sons Inc.",

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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 - 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 - 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

UR - https://www.scopus.com/pages/publications/84946409916

UR - https://www.scopus.com/pages/publications/84946409916#tab=citedBy

U2 - 10.1002/chem.201503595

DO - 10.1002/chem.201503595

M3 - Article

C2 - 26437692

AN - SCOPUS:84946409916

SN - 0947-6539

VL - 21

SP - 16781

EP - 16785

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 47

ER -

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

Abstract

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