The Catalytic Asymmetric Intermolecular Prins Reaction

Díaz-Oviedo, Christian; Maji, Rajat; List, Benjamin

doi:10.1021/jacs.1c10245

Cited by 26 publications

(16 citation statements)

References 57 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Because the ratio of products 26 and 27 reflects the starting material composition, both a stepwise and a highly asynchronous concerted pathway are plausible. On the basis of these studies and previous reports from our group 21 , 32 , the following catalytic cycle is proposed (Fig. 4d ).…”

Section: Mainsupporting

confidence: 61%

Catalytic asymmetric synthesis of cannabinoids and menthol from neral

Grimm

Zhou

Properzi

et al. 2023

Nature

Self Cite

View full text Add to dashboard Cite

The selective conversion of natural or synthetic neral to (1R,6S)-trans-isopiperitenol would enable and expedite sustainable routes to menthol1,2 and cannabinoids3–5. However, this reaction has been considered impossible because its product is more reactive to the required acid catalysts than its starting material, resulting in several side products6–9. We now show that an unsymmetric, strong and confined chiral acid, a highly fluorinated imino-imidodiphosphate, catalyses this process with excellent efficiency and selectivity. Expanding the method to other α,β-unsaturated aldehydes could enable access to new cannabinoids and menthol derivatives not readily accessible previously. Mechanistic studies suggest that the confined catalyst accomplishes this reaction by binding the product in an unreactive conformation, thereby preventing its decomposition. We also show how (1R,6S)-trans-isopiperitenol can be readily converted to pharmaceutically useful cannabinoids and menthol, each in the shortest and most atom-economic routes so far.

show abstract

Section: Mainsupporting

confidence: 61%

Catalytic asymmetric synthesis of cannabinoids and menthol from neral

Grimm

Zhou

Properzi

et al. 2023

Nature

Self Cite

View full text Add to dashboard Cite

show abstract

“…A more general strategy for performing a catalytic enantioselective Prins cyclization has been presented by List and co-workers, enabling the straightforward synthesis of tetrahydropyrans through the reaction between a simple homoallylic alcohol and an aliphatic or an (hetero)aromatic aldehyde ( Scheme 15 ). 20 In this particular case, the imino-imidodiphosphate catalyst participates in the reaction by catalyzing the process in a confined environment that enables a very efficient transfer of stereochemical information from the catalyst to the product. This methodology has been applied for the synthesis of several fragrances by simple hydrogenation of the exocyclic double bond.…”

Section: Enantioselective Prins Cyclizationmentioning

confidence: 99%

Recent Advances in the Prins Reaction

Reyes

Prieto²,

Uria³

et al. 2022

ACS Omega

View full text Add to dashboard Cite

The Prins reaction is a very convenient synthetic platform for the preparation of oxygen-containing heterocyclic compounds, especially tetrahydropyrans and tetrahydrofurans. While this reaction has been extensively used by synthetic chemists since its discovery, the last years have witnessed impressive improvements in its performance and scope and especially in the development of new catalytic and enantioselective versions. This mini-review presents these recent advances through selected representative examples.

show abstract

“…Replacing either the cyclohexane-1,2-diamine skeleton (R) or the 2″-phenyl moiety (R′) on the C 3 substituent in C6 with other substructures afforded inferior results (entries 7–11). The electronic and steric effects of 6,6′-substituents on binaphthalene moieties proved to be crucial to the chemo- and enantioselectivity, and C17 bearing adamantyl groups provided the best results (95% ee, Az/Ox/Cc = 10:1:1.9) (entries 12–17) . Replacing either NaN 3 or PhIO with another azide source or oxidant afforded inferior results (entry 18, see the Supporting Information for details).…”

Section: Resultsmentioning

confidence: 99%

Site- and Enantioselective Manganese-Catalyzed Benzylic C–H Azidation of Indolines

Cao

Wang

et al. 2022

J. Am. Chem. Soc.

View full text Add to dashboard Cite

A manganese-catalyzed highly site-and enantioselective benzylic C−H azidation of indolines has been described. The practical method is applicable for azidation of a tertiary benzylic C−H bond with good functional group tolerance, allowing facile access to structurally diverse tertiary azide-containing indolines in high efficiency with excellent site-, chemo-, and enantioselectivity. The generality of the method was further demonstrated by site-and enantioselective azidation of the secondary benzylic C−H bond for a range of secondary azide-containing indolines. The benzylic C−H azidation method allows to straightforwardly and enantioselectively install a variety of nitrogen-based functional groups and diverse bioactive molecules at the C 3 position of indoline frameworks through post-azidation manipulations. Gram-scale synthesis was also demonstrated, further highlighting the synthetic potential of the method. Mechanistic studies by combined experiments and computations elucidated the reaction mechanism and origins of stereoselectivity.

show abstract

The Catalytic Asymmetric Intermolecular Prins Reaction

Cited by 26 publications

References 57 publications

Catalytic asymmetric synthesis of cannabinoids and menthol from neral

Catalytic asymmetric synthesis of cannabinoids and menthol from neral

Recent Advances in the Prins Reaction

Site- and Enantioselective Manganese-Catalyzed Benzylic C–H Azidation of Indolines

Contact Info

Product

Resources

About