The first total synthesis of (−)-hosieine A was accomplished and features an unprecedented nitroso–ene cyclization to construct the 2-azabicyclo[3.2.1]octane ring system. Phosphine-enabled stereoselective bromohydrination provided interesting mechanistic insights into the anti-Markovnikov process. Also noteworthy is the retention of stereochemistry at C9 in the facile radical debromination initiated by Et₃B/air.

The first total synthesis of (−)-hosieine A was accomplished and features an unprecedented nitroso–ene cyclization to construct the 2-azabicyclo[3.2.1]octane ring system. Phosphine-enabled stereoselective bromohydrination provided interesting mechanistic insights into the anti-Markovnikov process. Also noteworthy is the retention of stereochemistry at C9 in the facile radical debromination initiated by Et₃B/air.

A rapid synthetic route toward (±)-Bakuchiol is presented in 29% overall yield. After the sole all-carbon quaternary carbon center is created via allylboration of 2-aryl acetaldehyde, a "Pot-Economy" approach including mesylation, elimination, and desilylation was realized in the presence of ^tBuOK under ambient temperature to provide (±)-Bakuchiol.

Polyketide antibiotics bearing skipped polyols represent a synthetic challenge. A SiCl₄-promoted oxonia-Cope rearrangement of syn,syn-2-vinyl-1,3-diols was developed to forge an array of 1,5-pentenediols, thus providing versatile motifs for the preparation of 1,2,3,5-stereoarrays in a highly stereoselective manner. Further exploration with Sn(OTf)₂ realized the rearrangement of a cross-aldehyde which tactically warrants the utility of the current approach to access complex polyketides. The origin of high stereoselectivity is attributed to a chairlike anti-conformation of the oxonium ion intermediate.

Polyketide antibiotics bearing skipped polyols represent a synthetic challenge. A SiCl₄-promoted oxonia-Cope rearrangement of syn,syn-2-vinyl-1,3-diols was developed to forge an array of 1,5-pentenediols, thus providing versatile motifs for the preparation of 1,2,3,5-stereoarrays in a highly stereoselective manner. Further exploration with Sn(OTf)₂ realized the rearrangement of a cross-aldehyde which tactically warrants the utility of the current approach to access complex polyketides. The origin of high stereoselectivity is attributed to a chairlike anti-conformation of the oxonium ion intermediate.

A concise synthesis of racemic Tapentadol and its stereoisomers was presented. The key step was a TiCl₄·THF₂-catalzyed aza-Belluš-Claisen rearrangement to create two vicinal tertiary carbon stereogenic centers. The subsequent reduction of amide and hydrogenation of alkene delivered Tapentadol and its stereoisomers. The current approach offers a practical synthetic route to access this class of pharmaceutically significant molecules.

Terpenoids comprise the largest family of natural products and include various structurally different genus which play important roles in living organisms. Biosynthetically, diterpenoids are derived from (E,E,E)-geranylgeranyl diphosphate (GGPP). From GGPP, diterpene cyclase catalyzes a sequence of carbocation-mediated cyclizations, rearrangements, and further oxidations, leading to a class of structurally unique ent-kaurenes, such as cafestol, gibberellin A3 and oridonin. According to the biosynthesis pathway of ent-kaurene, we designed a chiral acetal-enabled and SnCl₄-promoted biomimetic polyene cationic cyclization. With a following Birch reduction/alkylation cascade, a core skeleton of representative ent-kaurenes diterpenoids was completed.