Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 25, Issue 67, Pages 15411-15418Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201904028
Keywords
computational study; divergent synthesis; lactones; rearrangement; thiolation
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Funding
- NSFC [21871178, 21702135, 21871088]
- Chenguang Program - Shanghai Education Development Foundation [16CG22]
- Shanghai Municipal Education Commission
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A divergent strategy for the facile preparation of various enantioenriched phenylthio-substituted lactones was developed based on Lewis base/Bronsted acid co-catalyzed thiolation of homoallylic acids. The acid-controlled regiodivergent cyclization (6-endo vs. 5-exo) and acid-mediated stereoselective rearrangement of phenylthio-substituted lactones were explored. Experimental and computational studies were performed to clarify the origins of the regioselectivity and enantioselectivity. The calculation results suggest that C-O and C-S bond formation might occur simultaneously, without formation of a commonly supposed catalyst-coordinated thiiranium ion intermediate and the potential pi-pi stacking between substrate and SPh as an important factor in the enantio-determining step. Finally, this methodology was applied in the rapid syntheses of the bioactive natural products (+)-ricciocarpin A and (R)-dodecan-4-olide.
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