Metal-Associated Enols as Key Intermediates in Controlling Enantioselectivity in Carbene Insertion Reactions DOI
Garima Jindal,

Dipti K. Dodiya,

Mahesh Singh Harariya

и другие.

Synlett, Год журнала: 2025, Номер unknown

Опубликована: Март 11, 2025

Abstract Transition-metal-catalysed asymmetric carbene insertion reactions into various X–H bonds typically suffer from poor stereoselectivity. It has been proposed that the presence of metal-free intermediates leads to erosion selectivity. In current account, we discuss our recent efforts understand mechanism and stereochemical model Rh- Fe-catalysed indole phenol. Our detailed DFT calculations show all transformations adopt a common involving an enol intermediate, further tautomerisation which is key stereodetermining step. To account for enantioinduction, propose novel metal-associated species can be solving challenges in reactions. The geometry metal–enol complex interaction between chiral metal prochiral play important roles driving reaction toward particular stereoisomer. 1 Introduction 2 Rh-Catalysed Carbene Insertion Indole 3 Fe-Catalysed C–H Functionalisation 4 O–H 5 Conclusion

Язык: Английский

Computational Insights into “Lone Pair–Lone Pair Interaction-Controlled” Isomerization in the Asymmetric Total Syntheses of (+)-3-(Z)-Laureatin and (+)-3-(Z)-Isolaureatin DOI
Hyoungsu Kim, Deukjoon Kim, Jiyong Park

и другие.

The Journal of Organic Chemistry, Год журнала: 2025, Номер 90(4), С. 1531 - 1537

Опубликована: Янв. 16, 2025

Described herein is our computational study to rationalize the stereoselective epimerization of α,α'-cis-disubstituted oxolane and oxetane ketones 6 7 corresponding α,α'-trans 8 9 reported in previous total syntheses (+)-3-(Z)-isolaureatin (1) (+)-3-(Z)-laureatin (2). Density functional theory (DFT) calculations using appropriately truncated models revealed that are more stable than α,α'-cis ketones, very good agreement with experimental results. The results showed isomer a longer interatomic distance between two ring oxygen atoms was lower energy, which suggested presence repulsive interactions those atoms. Support for these distance-dependent came from observation energy differences isomers correlated solvent polarity. Most importantly, larger interoxygen difference could be responsible enhanced stereoselectivity ketone compared [0.25 Å (trans only) vs 0.13 (trans/cis = 4:1)].

Язык: Английский

Процитировано

0
Metal-Associated Enols as Key Intermediates in Controlling Enantioselectivity in Carbene Insertion Reactions DOI
Garima Jindal,

Dipti K. Dodiya,

Mahesh Singh Harariya

и другие.

Synlett, Год журнала: 2025, Номер unknown

Опубликована: Март 11, 2025

Abstract Transition-metal-catalysed asymmetric carbene insertion reactions into various X–H bonds typically suffer from poor stereoselectivity. It has been proposed that the presence of metal-free intermediates leads to erosion selectivity. In current account, we discuss our recent efforts understand mechanism and stereochemical model Rh- Fe-catalysed indole phenol. Our detailed DFT calculations show all transformations adopt a common involving an enol intermediate, further tautomerisation which is key stereodetermining step. To account for enantioinduction, propose novel metal-associated species can be solving challenges in reactions. The geometry metal–enol complex interaction between chiral metal prochiral play important roles driving reaction toward particular stereoisomer. 1 Introduction 2 Rh-Catalysed Carbene Insertion Indole 3 Fe-Catalysed C–H Functionalisation 4 O–H 5 Conclusion

Язык: Английский

Процитировано

0