Total synthesis of the monoterpenoid alkaloid (±)-tangutorine

A novel approach to a formal total synthesis of the monoterpenoid indole alkaloid (±)-tangutorine has been developed starting from an α,β-unsaturated cyclic dehydroamino ester. Synthesis of the rather unusual trans-substituted 2,3-indoloquinolizidine substructure was accomplished via Cu(II)-mediated conjugate addition and organozinc/copper coupling as the key steps, thereby setting the stage for ring-closing metathesis to produce the quinolone substructure. Finally, Bischler-Napieralski cyclization gave rise to the pentacyclic system of (±)-tangutorine thereby realizing a formal synthesis in an overall yield of 5.2% in eight consecutive steps.     

General approach for the stereocontrolled synthesis of tricyclic lactones via allene intramolecular cycloaddition. An application to the synthesis of (±)-platyphyllide

A new synthesis of tricyclic lactones via allene intramolecular cycloaddition and its application to synthesis of (±)-platyphyllide are described.     

An approach toward the synthesis of β-hydroxy sulfones on water

Various β-hydroxyl sulfones are prepared by regioselective ring opening of epoxides with sodium salt of sulfinate on water. This is an efficient protocol which avoids hazardous and moisture sensitive catalysts.     

A ring-closing metathesis approach for the synthesis of (±)-pregabalin

Abstract  

Efficient utilization of a Mannich-type reaction and the ring-closing metathesis (RCM) approach that leads to a convenient synthesis of 3-(aminomethyl)-5-methylhexanoic acid (pregabalin) is described.     

Allenyl azide cycloaddition chemistry: application to the total synthesis of (±)-meloscine

The pentacyclic alkaloid (±)-meloscine was prepared in 19 steps through a reaction sequence that features a putative azatrimethylenemethane intermediate, generated through cascade cyclization of an allenyl azide substrate, to deliver the core azabicyclo[3.3.0]octadiene substructure. Subsequent manipulation of the peripheral functionality then delivered (±)-meloscine.     

Formal total synthesis of (±)-estrone via the furano diene approach

We present in this report the development and realization of a novel formal total synthesis of estrone (1) via the Torgov diene (24) by the furano diene approach, first attempted by Woodward in 1937. The core ring structure 16 was established by an acid-mediated regioselective and stereospecific cyclization of the endo-oxabicyclo[2.2.1]heptene derivative 14, which is readily available from the AlCl(3)-catalyzed Diels-Alder cycloaddition of 2-(3-methoxyphenethyl)furan (4) and dimethyl maleate. The mechanistic pathway of this S(N)' type cyclization is discussed, and the earlier perspectives in our preliminary report (Org. Lett. 2004, 6, 1333) are corrected.     

An approach toward the alkaloid (±)-mersicarpine using a rhodium(II) carbenoid cyclization-cycloaddition cascade of an α-diazo dihydroindolinone

A tandem carbonyl ylide/1,3-dipolar cycloaddition cascade of α-diazo indole-2,3-dione with several different dipolarophiles was investigated. The intermolecular Rh(II)-catalyzed reaction occurs efficiently and affords dipolar cycloadducts in high yields. The analogous intramolecular reaction also takes place and gives an azapolycyclic product derived from trapping of the carbonyl ylide dipole with a tethered alkene. The power of the intramolecular cascade sequence is that it rapidly assembles polycyclic ring systems containing both multiple stereocenters and adjacent quaternary carbon centers in a single step in high yield. This cascade reaction was successfully utilized in a model study directed toward the total synthesis of mersicarpine.     

Stereoselective synthesis of (±)-tetraponerine-8, a defence alkaloid of the ant Tetraponera sp.

The title compound has been stereoselectively synthesized in 6 steps.     

Intramolecular Diels-Alder cycloaddition/rearrangement cascade of an amidofuran derivative for the synthesis of (±)-minfiensine

An efficient synthesis of (±)-minfiensine has been accomplished employing an intramolecular Diels-Alder cycloaddition/rearrangement cascade of an amidofuran derivative. Thermal reorganization of the initially formed [4+2]-cycloadduct affords the critical tetrahydroiminoethanocarbazole skeleton of the alkaloid in high yield.     

Total synthesis of the antiviral (±) virantmycin

A total synthesis of the antiviral metabolite virantmycin is described.     

An approach to the synthesis of 1,2λ-azaphosphinines

A novel approach to 1,2λ⁵-azaphosphinines has been elaborated. Aminophosphonium chlorides bearing a β-dialkylaminocrotonic nitrile residue react with N,N-dimethylformamide dimethylacetal to afford 1,2λ⁵-azaphosphinines.     

A convergent approach towards the synthesis of the 2-alkyl-substituted tetrahydroquinoline alkaloid (−)-cuspareine

A convergent approach towards the synthesis of the 2-alkyl-substituted tetrahydroquinoline alkaloid (?)-cuspareine via enantiospecific construction of the (R)-benzyl 2-formyl-3,4-dihydroquinoline-1(2H)-carboxylate. We have achieved an efficient enantiospecific synthesis of (?)-cuspareine starting from known key starting materials. The reactions employed for individual transformations are simple and high yielding, and the strategy could potentially be easily extended.     

Total synthesis of (±)-cephalosol

A concise and efficient total synthesis of (±)-cephalosol has been completed (5 steps from known ester 5, 39% overall yield), featuring a Cu(II)-promoted haloisocoumarin formation and sequential Suzuki cross-coupling/intramolecular oxo-Michael addition.     

The synthesis of (±)-cavernosine

The title compound and its epimer were synthesized in three and two steps from dihydro-β-ionone and 2-trimethylsiloxyfuran in 38 and 63% overall yields respectively. Their relative configurations were confirmed by X-ray of an intermediate.     

A synthesis of (±)-hymenin

(±)-Hymenin (1) has been synthesized by a highly efficient route involving the generation of an azafulvene intermediate and its coupling with 2-aminoimidazole.     

Regioselective synthesis of (±)-gabaculine

(±)-Gabaculine has been synthesized via an intramolecular reaction of an N-acyliminium intermediate with a propargyl silane, followed by allene ozonolysis and a Shapiro reaction.