Journal ArticleDOI
Biosynthetic consequences of multiple sequential post-transition-state bifurcations
Young J. Hong,Dean J. Tantillo +1 more
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TLDR
A system for which a single transition-state structure leads to the formation of many isomeric products via pathways that feature multiple sequential bifurcations is described, which redefine the challenges faced by nature in controlling the biosynthesis of complex natural products.Abstract:
A terpene-forming carbocation reaction is described for which a single transition-state structure leads to the formation of many isomeric products via pathways that feature multiple sequential bifurcations. Dynamic effects are shown to contribute to the selectivity of the reaction, with consequences for how enzymes control the biosynthesis of complex natural products.read more
Citations
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Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields
TL;DR: In this paper, the unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio using DFT, MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set.
Journal ArticleDOI
Structural and Chemical Biology of Terpenoid Cyclases.
TL;DR: Key advances in terpenoid cyclase structural and chemical biology are reviewed, focusing mainly on ter penoid cyclases and related prenyltransferases for which X-ray crystal structures have informed and advanced the authors' understanding of enzyme structure and function.
Journal ArticleDOI
Intrinsic reaction coordinate: Calculation, bifurcation, and automated search
TL;DR: The intrinsic reaction coordinate (IRC) approach has been used extensively in quantum chemical analysis and prediction of the mechanism of chemical reactions as mentioned in this paper, which gives a unique connection from a given transition structure to local minima of the reactant and product sides.
Journal ArticleDOI
Computational Organic Chemistry: Bridging Theory and Experiment in Establishing the Mechanisms of Chemical Reactions
TL;DR: The applications of various experimental techniques in elucidation of reaction details as well as the development of various computational techniques to meet the demand of emerging synthetic methods, e.g., C-H activation, organocatalysis, and single electron transfer are presented along with some conventional developments of mechanistic aspects.
Journal ArticleDOI
SAM-dependent enzyme-catalysed pericyclic reactions in natural product biosynthesis
Masao Ohashi,Fang Liu,Yang Hai,Mengbin Chen,Man-Cheng Tang,Zhongyue Yang,Michio Sato,Michio Sato,Kenji Watanabe,K. N. Houk,Yi Tang +10 more
TL;DR: A versatile S-adenosyl-l-methionine (SAM)-dependent enzyme, LepI, is reported that can catalyse stereoselective dehydration followed by three pericyclic transformations via a single ambimodal transition state, and a retro-Claisen rearrangement.
References
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Journal ArticleDOI
Density‐functional thermochemistry. III. The role of exact exchange
TL;DR: In this article, a semi-empirical exchange correlation functional with local spin density, gradient, and exact exchange terms was proposed. But this functional performed significantly better than previous functionals with gradient corrections only, and fits experimental atomization energies with an impressively small average absolute deviation of 2.4 kcal/mol.
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Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
TL;DR: Numerical calculations on a number of atoms, positive ions, and molecules, of both open- and closed-shell type, show that density-functional formulas for the correlation energy and correlation potential give correlation energies within a few percent.
Journal ArticleDOI
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
TL;DR: In this article, the unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio using DFT, MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set.
Journal ArticleDOI
A New Mixing of Hartree-Fock and Local Density-Functional Theories
TL;DR: In this article, a new coupling of Hartree-Fock theory with local density functional theory was proposed to improve the predictive power of the Hartree−Fock model for molecular bonding, and the results of tests on atomization energies, ionization potentials, and proton affinities were reported.
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Reaction Path Following in Mass-Weighted Internal Coordinates
TL;DR: In this article, the authors extended their previous algorithm for following reaction paths downhill to use mass-weighted internal coordinates, which has the correct tangent vector and curvature vectors in the limit or small step size but requires only the transition vector and the energy gradients.