An induced-fit model for asymmetric organocatalytic reactions: a case study of the activation of olefins via chiral Brønsted acid catalysts

Abstract

We elucidate the stereo-controlling factors of the asymmetric intramolecular hydroalkoxylation of terminal olefins catalyzed by bulky Brønsted acids [Science 2018, 359 (6383), 1501-1505] using high-level electronic structure methods. The catalyst-substrate...

Structurally divergent enantioselective synthesis of benzofuran fused azocine derivatives and spiro-cyclopentanone benzofurans enabled by sequential catalysis

“…2 show that % V free , which accounts for the percentage of total free volume within the catalyst pocket, has similar values. 18 However, a careful investigation reveals that % V free in the south-east quadrant, where the C-C coupling between the two substrates takes place is signicantly lower for TS re-SR (21.8%) as compared to that for TS re-SS (35.3%). A smaller value of % V free indicates greater connement and thereby more steric encumbrance.…”

The Role of Aromatic Alcohol Additives on Asymmetric Organocatalysis Reactions: Insights from Theory

“…We have used different methods i.e NCI, constraining the conformer etc. available with the CREST tool for performing an enhanced conformation sampling for the transition state calculations [43] . The full quantum chemical calculations using M06‐2X/TZVP/COSMO(CH 2 Cl 2 ) method to the CREST generated transitions state conformations do not generate any conformer that is more stable than the most stable transitions state conformer previously mentioned in the manuscript.…”

Molecular Understanding and Practical In Silico Catalyst Design in Computational Organocatalysis and Phase Transfer Catalysis—Challenges and Opportunities

“…These generally approximate the canonical CCSD(T) result for large molecules in the benchmark dataset described above. Bistoni and co-workers have reported the DLPNO-CCSD(T)/def2-TZVP single-point calculations for two computational studies on organocatalysis [ 37 , 40 ].…”

“…Blue Dash line: key bonds in TS. Three-dimensional representations are generated from coordinates given in the cited references: Paton 2018 [ 29 ]; Houk and Xue 2019 [ 30 ]; Goodman 2020 [ 31 ]; Kee and Wong 2020 [ 32 ]; Richmond 2020 [ 33 ]; Wheeler 2020 [ 34 ]; Papai 2020 [ 35 ]; Wong and Yang 2021 [ 36 ]; Sunoj 2022 [ 28 ]; Bistoni 2022 [ 37 ]; Champagne 2022 [ 38 ]; Knowles and Sigman 2022 [ 39 ].…”