The first and catalytic enantioselective total synthesis of hypocrolide A (>99% ee) in 12 steps, as well as other botryanes, is described. The absolute configurations of these compounds have been unambiguously confirmed or reassigned accordingly. The key reactions in this study include an unusual rhodium-catalyzed intramolecular [4 + 2] cycloaddition and a biomimetic oxidative [3 + 2] cycloaddition based on our revised biogenetic pathway.

A new method has been developed for the concise and asymmetric synthesis of seven humulanolides in 5–7 steps without the need for protecting groups. Notably, the challenging 11-membered ring and bridged butenolide moieties in asteriscunolide D and 6,7,9,10-tetrahydroasteriscunolide were introduced in one step using a ring-opening/ring-closing metathesis cascade reaction. Asteriscunolide D was used as a versatile synthetic precursor to prepare asteriscunolides A–C via a photoinduced isomerization reaction, asteriscanolide via a unique transannular Michael reaction, and 6,7,9,10-tetradehydroasteriscanolide via a transannular Morita–Baylis–Hillman-type reaction. The unique bicyclo[6.3.0]undecane core was introduced diastereoselectively.

The concise total synthesis of aplykurodinone-1 with an unusual cis-fused hydrindane moiety has been accomplished without the need for any protecting group chemistry using a unique SmI2 mediated reductive cascade cyclization reaction and a direct cuprate mediated 1,4-addition. This work represents the first example of the use of a SmI2-mediated intramolecular cascade cyclization reaction between “halide, alkene and aldehyde” groups.

Stereoselective synthesis of the trans-decalin subunit with a defined C1 quaternary chiral center has been achieved by the Pauson–Khand reaction (PKR) as a key step. The developed chemistry offers an alternative to the IMDA reaction that has been used for the syntheses of trans-decalin based biologically active natural products.

A total synthesis of the caribenol A (1), a novel natural product with an intriguing tetracyclic framework, has been achieved. The synthesis features an intramolecular Diels–Alder (IMDA) reaction for the facile construction of the tricyclic [5–7–6] skeleton of caribenol A (1) and a biomimetic oxidation reaction for the formation of the 2-hydroxyfuran-2(5H)-one motif of caribenol A (1) as key steps. This synthetic approach also reveals that the sp2 carbon at C(2) in substrate 8 is a critical factor for the formation of the tricyclic [5–7–6] skeleton in 7.

A concise synthetic pathway that enables the stereoselective construction of the tetracyclic core of nanolobatolide has been developed by applying a tandem ring-closing metathesis (RCM) reaction of dienynes, a Eu(fod)3-catalyzed intermolecular Diels–Alder reaction, and a biomimetic epoxide opening reaction as key steps.

Development of a gold-catalyzed tandem reaction of 1,7-diynes with both internal and external nucleophiles was realized, which constructed five chemical bonds, two rings, and two stereogenic centers in a single step. Based on the novel cascade transformation, we achieved a unified strategy toward the stereoselective total syntheses of C-15 oxygenated drimane-type sesquiterpenoids and their analogues, which provided the natural products kuehneromycin A, antrocin, anhydromarasmone, and marasmene as a proof-of-concept study.

A new strategy for the stereoselective total synthesis of natural product pseudolaric acid A (1) was accomplished in 16 steps from commercially available starting material, featuring a samarium diiodide (SmI2)-mediated intramolecular alkene-ketyl radical cyclization and a ring-closing metathesis (RCM) reaction to stereoselectively cast the unusual trans-fused [5–7]-bicyclic core of pseudolaric acid A (1).

A unified strategy toward the asymmetric facile construction of the [6.7.6.5]oxapentacyclic skeleton of cortistatins is reported, featuring intramolecular Diels−Alder (IMDA), oxidative dearomatization, and an oxy-Michael addition reaction.

A novel and concise approach for the construction of the core structure of maoecrystal V (1) has been developed. Utilizing the lead-mediated arylation of β-ketoesters and oxidative dearomatization/IMDA reaction as key steps, the two consecutive all-carbon quaternary centers (C-9 and C-10) were constructed in a stereoselective manner. The developed chemistry paves the way for the total synthesis of this fascinating natural product.

Stereoselective synthesis of the trans-decalin subunit with a defined C1 quaternary chiral center has been achieved by the Pauson–Khand reaction (PKR) as a key step. The developed chemistry offers an alternative to the IMDA reaction that has been used for the syntheses of trans-decalin based biologically active natural products.