The first total synthesis and structural validation of phosdiecin A was accomplished in 13 steps (LLS) through asymmetric iridium-catalyzed alcohol-mediated carbonyl reductive coupling. The present route is the shortest among >30 total and formal syntheses of fostriecin family members.

The total synthesis and structural revision of (+)-cryptoconcatone H are described. Guided by computational studies for the final structure assignment, the stereogenic centers at the tetrahydropyran moiety of (+)-cryptoconcatone H were assembled through catalytic asymmetric methodologies: Krische allylation, cross-metathesis reaction, and THP formation via Pd(II)-catalyzed cyclization. Finally, a Krische allylation reaction established the last stereocenter, and the lactone moiety was formed by ring-closing metathesis.

The structural, biological, and pharmacological profiles of phosphorylated secondary metabolites is presented. An overview of the phosphorylation methodologies employed in their total syntheses is also included.

The RhIII‐catalyzed allylic C−H alkynylation of non‐activated terminal alkenes leads selectively to linear 1,4‐enynes at room‐temperature. The catalytic system tolerates a wide range of functional groups without competing functionalization at other positions. Similarly, the vinylic C−H alkynylation of α,β‐ and β,γ‐ unsaturated amides gives conjugated Z‐1,3‐enynes and E‐enediynes.

Cyclometalated π-allyliridium C,O-benzoates modified by ( S)-SEGPHOS or ( S)-Cl,OMe-BIPHEP catalyze enantioselective 2-propanol-mediated reductive couplings of diverse nonmetallic allyl pronucleophiles with the acetylenic aldehyde TIPSC≡CCHO. Absolute stereochemistries of the resulting secondary homoallylic-propargylic alcohols were assigned using Rychnovsky's competing enantioselective conversion method.

Quantum chemical calculations of nuclear magnetic resonance (NMR) shifts and coupling constants have been extensively employed in recent years mainly to facilitate structural elucidation of organic molecules. When the results of such calculations are used to determine the most likely structure of a natural product in advance, guiding the subsequent synthetic work, the term "computer-guided synthesis" could be coined. This review article describes the most relevant examples from recent literature, highlighting the scope and limitations of this merged computational/experimental approach as well.

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The RhIII‐catalyzed allylic C−H alkynylation of non‐activated terminal alkenes leads selectively to linear 1,4‐enynes at room‐temperature. The catalytic system tolerates a wide range of functional groups without competing functionalization at other positions. Similarly, the vinylic C−H alkynylation of α,β‐ and β,γ‐ unsaturated amides gives conjugated Z‐1,3‐enynes and E‐enediynes.