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Author(s): Domingo LR; Aurell MJ; Arno M; Saez JA
Title: Toward an understanding of the acceleration of diels-alder reactions by a pseudo-intramolecular process achieved by molecular recognition. A DFT study
Source: JOURNAL OF ORGANIC CHEMISTRY 72 (11): 4220-4227
Date: 2007 MAY 25
Document Type: Journal : Article
DOI:
Language: English
Comment:
Address: Univ Valencia, Dept Quim Organ, E-46100 Valencia, Spain.
Reprint: Domingo, LR, Univ Valencia, Dept Quim Organ, Dr Moliner 50, E-46100
Valencia, Spain. E-mail: domingo@utopia.uv.es
Abstract: The pseudo-intramolecular Diels-Alder (DA) reaction between a 2-substituted furan (1) and a N-maleimide derivative (2) has been analyzed using DFT methods. Formation of two hydrogen bonds between the appendages on furan and maleimide derivatives favors thermodynamically the formation of a molecular complex (MC1) through an efficient molecular recognition process. The large enthalpy stabilization associated with the molecular recognition overcomes the unfavorable activation entropy associated with the bimolecular process. As a consequence, the subsequent DA reaction is clearly accelerated through a pseudo-intramolecular process.
Cited References: ARROYO P, 2005, TETRAHEDRON, V61, P7359 BACH RD, 1989, J ORG CHEM, V54, P2931 BACHRACH SM, 1992, J ORG CHEM, V57, P6736 BACHRACH SM, 1994, J ORG CHEM, V59, P5027 BADER RFW, 1985, ACCOUNTS CHEM RES, V18, P9 BADER RFW, 1990, ATOMS MOL QUANTUM TH BENNES R, 1999, ORG LETT, V1, P1087 CARRUTHERS W, 1978, SOME MODERN METHODS CARRUTHERS W, 1990, CYCLOADDITION REACTI CAYZER TN, 2002, CHEM-EUR J, V8, P739 CAYZER TN, 2005, J ORG CHEM, V70, P5561 CHECK CE, 2005, J ORG CHEM, V70, P9828 DIELS O, 1928, LIEBIGS ANN CHEM, V460, P98 DOMINGO LR, 1997, J ORG CHEM, V62, P1662 DOMINGO LR, 1998, J AM CHEM SOC, V120, P1617 DOMINGO LR, 2002, J ORG CHEM, V67, P959 DOMINGO LR, 2002, TETRAHEDRON, V58, P4417 DOMINGO LR, 2003, J ORG CHEM, V68, P2895 DOMINGO LR, 2003, J ORG CHEM, V68, P3884 DOMINGO LR, 2003, J ORG CHEM, V68, P8662 ESS DH, 2006, ADV SYNTH CATAL, V348, P2337 GERRLINGS P, 2003, CHEM REV, V103, P1793 GOLDSTEIN E, 1996, J AM CHEM SOC, V118, P6036 IZGORODINA EI, 2005, J PHYS CHEM A, V109, P7558 JORGENSEN WL, 1993, J AM CHEM SOC, V115, P2936 KHUONG KS, 2005, J AM CHEM SOC, V127, P3688 LI Y, 1993, J AM CHEM SOC, V115, P7478 LIMANTO J, 2002, J AM CHEM SOC, V124, P14748 PADDONROW MN, 2005, J ORG CHEM, V70, P10841 PADWA A, 2006, J ORG CHEM, V71, P5432 PARR RG, 1999, J AM CHEM SOC, V121, P1922 PEARSON EL, 2006, J ORG CHEM, V71, P6099 PEARSON RJ, 2004, ORG BIOMOL CHEM, V2, P3434 PEARSON RJ, 2004, TETRAHEDRON LETT, V45, P4777 PEREZ P, 2006, THEORETICAL ASPECTS, V19, P167 PHILP D, 1998, CHEM COMMUN 0421, P879 POLO V, 2005, J PHYS CHEM A, V109, P10438 ROBERTSON A, 1999, TETRAHEDRON, V55, P11365 ROWLEY D, 1951, DISCUSS FARADAY SOC, P198 SU MD, 2004, ORGANOMETALLICS, V23, P2507 TANTILLO DJ, 2001, J ORG CHEM, V66, P1938 WOODWARD RB, 1969, ANGEW CHEM INT EDIT, V8, P781 |