An efficient stereoselective synthetic approach to colomitides, 2,7-dioxabicyclo[3.2.1]octane-type natural products, is reported. Key steps are a stereocontrolled aldol reaction and a gold-catalyzed cycloisomerization. This synthetic strategy has been applied for the first asymmetric total synthesis of the proposed colomitides and their possible diastereomers. Comparison of their 1H and 13C NMR spectra and specific rotations with those of the natural product revealed that the structure of colomitide A should be revised to 1c, and that the absolute stereochemistries of colomitides A and B are 2′R,4R,5R,8S,1R and 2′R,4S,5R,8S,1R.

(±)-Lingzhiol has been synthesized from commercially available 5,8-dimethoxytetralone in seven steps with an overall yield of 10.3% via an unprecedented acid-catalyzed semipinacol-type rearrangement. In addition, a novel strategy for the construction of the tetracyclic 5/5/6/6 core structure of lingzhiol has been developed via a tandem rearrangement/reduction/lactonization reaction.

The relative and absolute configurations of xiamenmycin A, a benzopyran compound isolated from Streptomyces xiamenensis 318 with a highly potent anti-fibrotic activity, have been characterized through the total synthesis. The key steps include the construction of the 3-chromanol moiety via Sharpless epoxidation followed by regio- and diastereo-selective cyclization and introduction of the threonine moiety at a later stage via Pd-catalysed aminocarbonylation in a one-pot procedure. The stereochemical assignment of natural xiamenmycin A has been accordingly revised to be 2R, 3S, 3′S, 4′R.

A novel formal synthesis of Beraprost (1) is described. The tricyclic cyclopent[b]benzofuran core is efficiently prepared from (−)-Corey lactone diol in 12 steps with an overall yield of 37.4%. Key features of the strategy include a ring-closing metathesis reaction and aromatization to form the tricyclic cyclopenta[b]benzofuran framework, and selective halogenation/formylation to install the butyrate side-chain.

The first total synthesis of benzonaphthyridine alkaloid (1), a unique diazaphenathrene alkaloid isolated from mangrove-derived Streptomyces albogriseolus, was accomplished. The core structure was unequivocally constructed via several key transformations, such as Knoevenagel condensation, Curtius rearrangement, and cyclic carbamate formation–reduction sequence. The chiral unsaturated ketone acid moiety was synthesized from N-tert-butoxycarbonyl-l-glutamic acid gamma-tert-butyl ester (15). The absolute configuration was determined.

A practical synthesis of Entecavir (1) has been accomplished in 10 steps with 21% overall yield. The key steps to construct the five-membered carbocyclic framework 2 are a ring-closing metathesis and a diethyl-aluminum 2,2,6,6-tetramethyl piperidide (DA-TMS) mediated epoxide isomerization. Furthermore, the guanine was introduced by modified Mitsunobu reaction.

A simple and five steps total synthesis of Ammosamide B has been developed. The tricyclic pyrroloquinoline in Ammosamides was constructed in one step based on Doebner–Miller reaction between 1,3-diamine-4,6-dinitrobenzene 8 and dimethyl-2-oxo glutaconate 9.

A novel formal synthesis of Beraprost (1) is described. The tricyclic cyclopent[b]benzofuran core is efficiently prepared from (−)-Corey lactone diol in 12 steps with an overall yield of 37.4%. Key features of the strategy include a ring-closing metathesis reaction and aromatization to form the tricyclic cyclopenta[b]benzofuran framework, and selective halogenation/formylation to install the butyrate side-chain.

An efficient stereoselective synthetic approach to colomitides, 2,7-dioxabicyclo[3.2.1]octane-type natural products, is reported. Key steps are a stereocontrolled aldol reaction and a gold-catalyzed cycloisomerization. This synthetic strategy has been applied for the first asymmetric total synthesis of the proposed colomitides and their possible diastereomers. Comparison of their 1H and 13C NMR spectra and specific rotations with those of the natural product revealed that the structure of colomitide A should be revised to 1c, and that the absolute stereochemistries of colomitides A and B are 2′R,4R,5R,8S,1R and 2′R,4S,5R,8S,1R.

The relative and absolute configurations of xiamenmycin A, a benzopyran compound isolated from Streptomyces xiamenensis 318 with a highly potent anti-fibrotic activity, have been characterized through the total synthesis. The key steps include the construction of the 3-chromanol moiety via Sharpless epoxidation followed by regio- and diastereo-selective cyclization and introduction of the threonine moiety at a later stage via Pd-catalysed aminocarbonylation in a one-pot procedure. The stereochemical assignment of natural xiamenmycin A has been accordingly revised to be 2R, 3S, 3′S, 4′R.