Special Organic Chemistry Seminar

Computational quantum chemistry has been increasingly employed toward rationalizing the stereochemical course of a diverse range of catalytic reactions.¹ The approach typically involves the identification of kinetically significant transition states and intermediates. In our laboratory, ab initio as well as DFT methods are employed to gain insights into carbon-carbon and carbon-heteroatom bond-forming reactions of immediate practical significance.² The key objective of our research is to gain molecular insights on the factors responsible for stereoselectivity and to exploit such insights toward in silico design of novel asymmetric catalysts.³ In other words, our research is motivated by past experiments while our results are meant to motivate future experiments.

A number of examples wherein the conventional transition state models required systematic improvements toward accounting the observed product distribution and stereochemical outcome will be presented. In general, the presentation would encompass a few contemporary themes in the domain of organocatalysis, transition metal catalysis, and cooperative multi-catalytic reactions.⁴ Interesting interpretations/rationalizations of experimental observations besides meaningful guidelines for rational improvements in the design of asymmetric catalysts would remain the key focus of the presentation. The contents are designed to cater a broad and diverse group of audience; hence, the chemical insights would be emphasized, rather than a labyrinth of technical details.

[1] (a) Cheong, P. H. –Y.; Legault, C. Y.; Um, J. M.; Celebi-Olcum, N.; Houk, K. N. Chem. Rev. 2011, 111, 5042. (b) Sunoj, R. B. Wiley Interdisciplinary Reviews: Comput. Mol. Sci. 2011, 1, 920.

[2] (a) Shinisha, C. B.; Sunoj, R. B. J. Am. Chem. Soc. 2010, 132, 12135. (b) Sharma, A. K.; Sunoj, R. B. Angew. Chem. Int. Ed. 2010, 49, 9373. (c) Jindal, G.; Sunoj, R. B. Angew. Chem., Int. Ed. 2014, 53, 4432. (d) Anand, M.; Sunoj, R. B.; Schaefer, H. F. J. Am. Chem. Soc. 2014, 136, 5535.

[3] (a) Shinisha, C. B.; Sunoj, R. B. Org. Biomol. Chem. 2007, 5, 1287. (b) Shinisha, C. B.; Sunoj, R. B. Org. Lett. 2009, 11, 3242. (c) Jindal, G.; Sunoj, R. B. Org. Bimol. Chem. 2014, 12, 2745.

[4] (a) Jindal, G.; Sunoj, R. B. J. Am. Chem. Soc. 2014, 136, 15998. (b) Jindal, G.; Kisan, H. K.; Sunoj, R. B. ACS Catal. 2015, 5, 480. (c) Reddi, Y.; Sunoj, R. B. ACS Catal. 2015 (DOI: 10.1021/cs502006x). (d) Kisan, H. K.; Sunoj, R. B. Chem. Commun. 2014, 50, 14639. (e) Kisan, H. K.; Sunoj, R. B. J. Org. Chem. 2015, (DOI: 10.1021/jo5027029)