Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 82, Issue 16, Pages 8464-8475Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.7b01211
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Funding
- DGAPA-UNAM [IN202915]
- CONACyT [219925, 587265, 576662]
- DGAPA-UNAM
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A stereodivergent C-glycosidation of carbohydrate derived lactones can be mediated by the protecting groups and applied to the total synthesis of (+)-varitriol and of two diastereoisomers thereof, which represent an unprecedent use of the protecting groups in the synthesis of a naturally occurring compound. In particular, the stereoselective nucleophile attack for 2,3-trans-substituted five-membered ring oxocarbenium ions is strongly influenced by the presence of aromatic rings in the protecting groups. According to quantum chemical calculations, the stereoselectvity depends on the pi-pi interactions between the aromatic ring of the C-2 protecting group with the exocyclic triple bond and the oxocarbenium ion. These interactions account for the stabilization of the conformer in which the C-2 and C-3 substituents adopt pseudoaxial orientations. When protecting groups do not contain an aromatic ring, the steroehemical outcome is dictated by stereoelectronic factors established by the Woerpel's model. Based on these findings, a concise total synthesis of the natural product (+)-varitriol and of two diastereoisomers was acomplished.
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