How the Proximal Pocket May Influence the Enantiospecificities of Chloroperoxidase-Catalyzed Epoxidations of Olefins
Abstract
:1. Introduction
2. Computational Details
2.1. Methods
2.2. CPO-I Models
2.3. Initial Structures for 1R2S and 1S2R CPO-I/CBMS Transition State Complexes
3. Results
4. Discussion
5. Conclusions
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Natural Spin Densities/Natural Atomic Charges | Bond Lengths | |||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
S–R | Por | Fe | O | CβH | CαH | R1+ | R2+ | S–Fe | Fe–O | O–Cβ | ||
1S2R | ||||||||||||
R | A | −0.75/−0.05 | −0.30/−0.49 | 1.10/0.91 | 0.95/−0.37 | 0.00/0.06 | 0.00/−0.03 | 0.00/−0.05 | 0.00/0.02 | 2.619 | 1.623 | – |
B | −0.60/−0.27 | −0.50/−0.32 | 1.15/0.95 | 0.95/−0.36 | 0.00/0.06 | 0.00/−0.03 | 0.00/−0.05 | 0.00/0.02 | 2.776 | 1.619 | – | |
TS | A | −0.70/−0.08 | −0.30/−0.58 | 0.95/0.90 | 0.75/−0.44 | −0.10/0.15 | 0.30/0.04 | 0.10/−0.02 | 0.00/0.03 | 2.554 | 1.705 | 1.985 |
B | −0.30/−0.40 | −0.25/−0.51 | 1.40/0.96 | 0.50/−0.42 | −0.05/0.18 | −0.20/0.08 | −0.10/0.07 | 0.00/0.04 | 2.570 | 1.658 | 2.099 | |
1R2S | ||||||||||||
R | A | −0.76/−0.05 | −0.30/−0.49 | 1.10/0.91 | 0.96/−0.37 | 0.00/0.06 | 0.00/−0.03 | 0.00/−0.05 | 0.00/0.02 | 2.624 | 1.623 | – |
B | −0.59/−0.27 | −0.48/−0.32 | 1.15/0.95 | 0.95/−0.36 | 0.00/0.06 | 0.00/−0.03 | 0.00/−0.05 | 0.00/0.02 | 2.776 | 1.619 | – | |
TS | A | −0.65/−0.08 | −0.28/−0.59 | 0.91/0.89 | 0.76/−0.43 | −0.11/0.15 | 0.27/0.05 | 0.10/−0.01 | 0.00/0.03 | 2.512 | 1.702 | 1.996 |
B | −0.30/−0.41 | −0.26/−0.50 | 1.38/0.96 | 0.52/−0.42 | −0.06/0.18 | −0.17/0.08 | −0.11/0.07 | 0.00/0.04 | 2.576 | 1.658 | 2.116 |
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Morozov, A.N.; Chatfield, D.C. How the Proximal Pocket May Influence the Enantiospecificities of Chloroperoxidase-Catalyzed Epoxidations of Olefins. Int. J. Mol. Sci. 2016, 17, 1297. https://doi.org/10.3390/ijms17081297
Morozov AN, Chatfield DC. How the Proximal Pocket May Influence the Enantiospecificities of Chloroperoxidase-Catalyzed Epoxidations of Olefins. International Journal of Molecular Sciences. 2016; 17(8):1297. https://doi.org/10.3390/ijms17081297
Chicago/Turabian StyleMorozov, Alexander N., and David C. Chatfield. 2016. "How the Proximal Pocket May Influence the Enantiospecificities of Chloroperoxidase-Catalyzed Epoxidations of Olefins" International Journal of Molecular Sciences 17, no. 8: 1297. https://doi.org/10.3390/ijms17081297