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WIREs Comput Mol Sci
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Organocatalysis: acylation catalysts

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Abstract This review shows how experimental and theoretical methods can help chemists to clarify the mechanism of acylation reactions and subsequently use this insight to develop improved acylation catalysts. Theoretical methods can be used in this context in a variety of ways, starting from the structural optimization of reactants, products, and reaction intermediates up to the full characterization of potential energy surfaces. Whether, in the end, all of this is necessary for the theory‐guided development of acylation catalysts is discussed in the last section of this review. The most challenging area in acylation catalyst development remains that of stereoselective catalysis, in which major advances have recently been made, but where theoretical prediction of catalyst selectivity is still exceedingly rare. © 2011 John Wiley & Sons, Ltd. WIREs Comput Mol Sci 2011 1 601–619 DOI: 10.1002/wcms.48 This article is categorized under: Structure and Mechanism > Molecular Structures

Possible mechanisms of the base‐catalyzed ester hydrolysis.

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Schreiner's catalyst 4794 and Birman's amidine‐based catalyst 48 with the transition state model 49 for the KR of alcohols99 (distances are given in picometer).

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Structures of pyridines studied by Zipse52,54,88,89 and Han,91,92 ordered by their relative acylation enthalpies, calculated at B3LYP/6–311+G(d,p)//B3LYP/6–31G(d) level. Data for 4‐aminopyridines 1, 2, and 3 are also shown.

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Model isodesmic reaction used for the development of new acylation catalysts.

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Structures of chiral catalysts used for the kinetic resolution of alcohols.78 Distances between the center of the pyridine ring and selected substituents are given in picometer.

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(a) Nucleophilic catalysis by TBD (31) for the transesterification and amidation of esters; (b) enthalpy profile for the base‐catalyzed aminolysis of methyl acetate as calculated at the MP2/6–311++G(d,p)//B3LYP/6–311++G(d,p) level of theory with IEF‐PCM modeling of toluene solvent effects.68

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Free energy profile for the TBD‐catalyzed methanolysis of δ‐valerolactone 32 as calculated at the B3LYP/6–311++G**//B3LYP/6–31+G* level of theory63 (distances are given in picometer).

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Structures of transition state 26 for the DMAP‐catalyzed methanolysis of l‐lactide 22, as calculated at B3LYP/6–31G(d) level,62 and transition state 29 for the TBD‐catalyzed methanolysis of l‐lactide, as calculated at MPW1K/6–31+G(d) level65 (distances are given in picometer).

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Nucleophilic (A) and basic (B) routes of activation in the DMAP‐catalyzed ring‐opening of l‐lactide by methanol as calculated at the B3LYP/6–31G(d) level of theory (PCM/SCRF single‐point calculations, including zero‐point vibrational energy corrections)62.

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Gas‐phase enthalpy profile (ΔH298, kJ/mol) for the competing nucleophilic and base catalysis mechanisms in the DMAP‐catalyzed reaction of acetic anhydride with tert‐butanol as calculated at the B3LYP/6–311+G(d,p)//B3LYP/6–31G(d) level of theory59 (distances are given in picometer).

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Nucleophilic mechanism of alcohol esterification catalyzed by DMAP; the structure shown for ion‐pair intermediate 10a has been obtained at UAHF‐PCM B3LYP/6–31G(d) level60 (distances are given in picometer).

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Relative catalytic activities of substituted pyridines in acylation reactions.45,46,52,54,55

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Free energy profile for two pathways in the acid‐catalyzed reaction of succinic anhydride with methylamine as calculated at PCM/B3LYP/6–31G(d) (benzene) level; geometrical parameters of the rate‐determining transition states are included23 (distances are given in picometer).

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Transition state structures for the acetylation of methanol as calculated at MP2/6–31+G(d,p) level (a)22 and the aminolysis of succinic anhydride: uncatalyzed (b) and catalyzed by methylamine (c) as calculated at B3LYP/6–31G(d) level23 (distances are given in picometer).

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