Brønsted acid catalyzed morita-baylis-hillman reaction: A new mechanistic view for thioureas revealed by ESI-MS(/MS) monitoring and DFT calculations

Giovanni W. Amarante; Mario Benassi; Humberto M.S. Milagre; Ataualpa A.C. Braga; Feliu Maseras; Marcos N. Eberlin; Fernando Coelho

doi:10.1002/chem.200900966

Brønsted acid catalyzed morita-baylis-hillman reaction: A new mechanistic view for thioureas revealed by ESI-MS(/MS) monitoring and DFT calculations

Giovanni W. Amarante, Mario Benassi, Humberto M.S. Milagre, Ataualpa A.C. Braga, Feliu Maseras, Marcos N. Eberlin, Fernando Coelho

Department of Chemistry

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

70 Citations (Scopus)

Abstract

A Morita-Baylis-Hillman (MBH) reaction catalyzed by thiourea was monitored by ESI-MS (/MS) and key intermediates were intercepted and characterized. These intermediates suggest that thiourea acts as an organocatalyst in all steps of the MBH reaction cycle, including the rate-limiting proton-transfer step. DFT calculations, performed for a model MBH reaction between formaldehyde and acrolein with trimethylamine as base and in the presence or the absence of thiourea, suggest that thiourea accelerates MBH reactions by decreasing the transitionstate (TS) energies through bidentate hydrogen bonding throughout the whole catalytic cycle. In the rate-limiting proton-transfer step, the thiourea acts not as a proton shuttle, but as a Brønsted acid stabilizing the basic oxygen center that is formed in the TS. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

Original language	English
Pages (from-to)	12460-12469
Journal	Chemistry - A European Journal
Volume	15
Issue number	45
DOIs	https://doi.org/10.1002/chem.200900966
Publication status	Published - 1 Jan 2009

Keywords

Density functional calculations
ESI mass spectrometry
Morita-baylis-hiliman reaction
Reaction mechanisms
Thiourea

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10.1002/chem.200900966

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Amarante, Giovanni W. ; Benassi, Mario ; Milagre, Humberto M.S. ; Braga, Ataualpa A.C. ; Maseras, Feliu ; Eberlin, Marcos N. ; Coelho, Fernando. / Brønsted acid catalyzed morita-baylis-hillman reaction: A new mechanistic view for thioureas revealed by ESI-MS(/MS) monitoring and DFT calculations. In: Chemistry - A European Journal. 2009 ; Vol. 15, No. 45. pp. 12460-12469.

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title = "Br{\o}nsted acid catalyzed morita-baylis-hillman reaction: A new mechanistic view for thioureas revealed by ESI-MS(/MS) monitoring and DFT calculations",

abstract = "A Morita-Baylis-Hillman (MBH) reaction catalyzed by thiourea was monitored by ESI-MS (/MS) and key intermediates were intercepted and characterized. These intermediates suggest that thiourea acts as an organocatalyst in all steps of the MBH reaction cycle, including the rate-limiting proton-transfer step. DFT calculations, performed for a model MBH reaction between formaldehyde and acrolein with trimethylamine as base and in the presence or the absence of thiourea, suggest that thiourea accelerates MBH reactions by decreasing the transitionstate (TS) energies through bidentate hydrogen bonding throughout the whole catalytic cycle. In the rate-limiting proton-transfer step, the thiourea acts not as a proton shuttle, but as a Br{\o}nsted acid stabilizing the basic oxygen center that is formed in the TS. {\textcopyright} 2009 Wiley-VCH Verlag GmbH & Co. KGaA.",

keywords = "Density functional calculations, ESI mass spectrometry, Morita-baylis-hiliman reaction, Reaction mechanisms, Thiourea",

author = "Amarante, {Giovanni W.} and Mario Benassi and Milagre, {Humberto M.S.} and Braga, {Ataualpa A.C.} and Feliu Maseras and Eberlin, {Marcos N.} and Fernando Coelho",

year = "2009",

month = jan,

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doi = "10.1002/chem.200900966",

language = "English",

volume = "15",

pages = "12460--12469",

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Brønsted acid catalyzed morita-baylis-hillman reaction: A new mechanistic view for thioureas revealed by ESI-MS(/MS) monitoring and DFT calculations. / Amarante, Giovanni W.; Benassi, Mario; Milagre, Humberto M.S.; Braga, Ataualpa A.C.; Maseras, Feliu; Eberlin, Marcos N.; Coelho, Fernando.

In: Chemistry - A European Journal, Vol. 15, No. 45, 01.01.2009, p. 12460-12469.

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

TY - JOUR

T1 - Brønsted acid catalyzed morita-baylis-hillman reaction: A new mechanistic view for thioureas revealed by ESI-MS(/MS) monitoring and DFT calculations

AU - Amarante, Giovanni W.

AU - Benassi, Mario

AU - Milagre, Humberto M.S.

AU - Braga, Ataualpa A.C.

AU - Maseras, Feliu

AU - Eberlin, Marcos N.

AU - Coelho, Fernando

PY - 2009/1/1

Y1 - 2009/1/1

N2 - A Morita-Baylis-Hillman (MBH) reaction catalyzed by thiourea was monitored by ESI-MS (/MS) and key intermediates were intercepted and characterized. These intermediates suggest that thiourea acts as an organocatalyst in all steps of the MBH reaction cycle, including the rate-limiting proton-transfer step. DFT calculations, performed for a model MBH reaction between formaldehyde and acrolein with trimethylamine as base and in the presence or the absence of thiourea, suggest that thiourea accelerates MBH reactions by decreasing the transitionstate (TS) energies through bidentate hydrogen bonding throughout the whole catalytic cycle. In the rate-limiting proton-transfer step, the thiourea acts not as a proton shuttle, but as a Brønsted acid stabilizing the basic oxygen center that is formed in the TS. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

AB - A Morita-Baylis-Hillman (MBH) reaction catalyzed by thiourea was monitored by ESI-MS (/MS) and key intermediates were intercepted and characterized. These intermediates suggest that thiourea acts as an organocatalyst in all steps of the MBH reaction cycle, including the rate-limiting proton-transfer step. DFT calculations, performed for a model MBH reaction between formaldehyde and acrolein with trimethylamine as base and in the presence or the absence of thiourea, suggest that thiourea accelerates MBH reactions by decreasing the transitionstate (TS) energies through bidentate hydrogen bonding throughout the whole catalytic cycle. In the rate-limiting proton-transfer step, the thiourea acts not as a proton shuttle, but as a Brønsted acid stabilizing the basic oxygen center that is formed in the TS. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

KW - Density functional calculations

KW - ESI mass spectrometry

KW - Morita-baylis-hiliman reaction

KW - Reaction mechanisms

KW - Thiourea

U2 - 10.1002/chem.200900966

DO - 10.1002/chem.200900966

M3 - Article

VL - 15

SP - 12460

EP - 12469

IS - 45

ER -

Brønsted acid catalyzed morita-baylis-hillman reaction: A new mechanistic view for thioureas revealed by ESI-MS(/MS) monitoring and DFT calculations

Abstract

Keywords

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