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
SN - 0947-6539
VL - 15
SP - 12460
EP - 12469
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 45
ER -