Total Synthesis of (−)-Dihydrosporothriolide Utilizing an Indium-Mediated Reformatsky–Claisen Rearrangement

The asymmetric synthesis of (−)-dihydrosporothriolide (<b>1</b>), a biologically active bis-γ-butyrolactone, is described, that proceeds through a d-proline-catalyzed asymmetric aminooxylation, indium-mediated Reformatsky–Claisen rearrangement of an α,α-dibromoacetate derivative, and diastereoselective dihydroxylation. The route requires no protective group manipulation and allows the concise seven-step synthesis of <b>1</b> from <i>n</i>-octanal

Total Synthesis of (−)-Kaitocephalin Based on a Rh-Catalyzed C–H Amination

A total synthesis of (−)-kaitocephalin, an ionotropic glutamate receptor antagonist, is accomplished in highly stereocontrolled manner via Overman rearrangement, rhodium-catalyzed benzylic C–H amination, pyrrolidine formation involving nucleophilic opening of a cyclic sulfamate, and rhodium-catalyzed allylic C–H amination as key steps

Total Synthesis of (−)‑<i>N</i>‑Methylwelwitindolinone C Isothiocyanate Based on a Pd-Catalyzed Tandem Enolate Coupling Strategy

The highly stereocontrolled total synthesis of (−)-<i>N</i>-methylwelwitindolinone C isothiocyanate is described, which features the expeditious construction of a bicyclo[4.3.1]­decane ring system by a palladium-catalyzed tandem enolate allylation/arylation reaction

Lewis Acid Template-Catalyzed Asymmetric Diels–Alder Reaction

An asymmetric Diels–Alder reaction of 2,4-dienols and methyl acrylate utilizing a chiral Zn­(II)/Mg­(II) bimetallic template with low catalyst loading was successfully achieved. The bimetallic Lewis acid template derived from (<i>R</i>)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-bi-2-naphthol catalyzed the Diels–Alder reaction in the presence of molecular sieves 4 Å to afford various functionalized bicyclic γ-lactones with high enantiomeric purities

Formal [4 + 1]-Cycloaddition of Homopropargyl Alcohols to Diazo Dicarbonyl Compounds Giving Substituted Tetrahydrofurans

A novel formal [4 + 1]-cycloaddition of readily available homopropargyl alcohols with diazo dicarbonyl compounds is described, which involves tandem O–H insertion/Conia-ene cyclization under cooperative Rh­(II)/Zn­(II) catalysis. This reaction provides easy access to various substituted tetra­hydro­furans and exhibits complete <i>E</i>-selectivity in the case of nonterminal alkynes

Total Synthesis of (−)-Cinatrin C₁ Based on an In(OTf)₃‑Catalyzed Conia-Ene Reaction

The stereocontrolled total synthesis of (−)-cinatrin C₁, a phospholipase A₂ inhibitor, has been accomplished. The key feature includes the stereoselective construction of the highly substituted tetrahydrofuran core by In­(OTf)₃-catalyzed Conia–ene reaction of the oxygen-tethered acetylenic malonic ester followed by dihydroxylation with concomitant lactonization

Stereocontrolled Total Synthesis of (−)-Englerin A

The total synthesis of (−)-englerin A, a potent and selective inhibitor of renal cancer cell lines, is described. The key feature includes the stereocontrolled construction of the cyclopentane structure by taking advantage of a base-promoted epoxynitrile cyclization

Total Synthesis of (−)-Cinatrin C₁ Based on an In(OTf)₃‑Catalyzed Conia-Ene Reaction

The stereocontrolled total synthesis of (−)-cinatrin C₁, a phospholipase A₂ inhibitor, has been accomplished. The key feature includes the stereoselective construction of the highly substituted tetrahydrofuran core by In­(OTf)₃-catalyzed Conia–ene reaction of the oxygen-tethered acetylenic malonic ester followed by dihydroxylation with concomitant lactonization

The Absolute Configuration for Inthomycin C: Revision of Previously Published Work with a Reinstatement of the (3<i>R</i>)‑Configuration for (−)-Inthomycin C

Stereochemical evidence is presented to demonstrate that (−)-inthomycin C has (3<i>R</i>)- and not (3<i>S</i>)-stereochemistry. Careful reappraisal of the previously published work− now indicates that the Hatakeyama, Hale, Ryu, and Taylor teams <i>all</i> have synthesized (−)-(3<i>R</i>)-inthomycin C. The newly measured [α]_D of pure (−)-(3<i>R</i>)-inthomycin C (98% ee) is −7.9 (<i>c</i> 0.33, CHCl₃) and not −41.5 (<i>c</i> 0.1, CHCl₃) as was previously reported in 2012