Studies towards the total synthesis of hygrocins A and B

The western segment of hygrocins A–B has been synthesized through the coupling of a chiral C5–C13 synthon with the sterically demanding hexasubstituted naphthalenic core. The C5–C13 chiral fragment has been assembled via a stereoselective Johnson orthoester rearrangement of an optically pure allylic alcohol derived from d-glucose. Our studies lay the platform for the determination of the absolute configuration of the unassigned C8-stereocenter of the title compounds in addition to the completion of the total synthesis of the unique ansamacrolides hygrocins A and B.     

Total synthesis of costatone: a monoterpene from the red seaweed: plocarnium costatum

The total synthesis of a unique, naturally occurring monoterpene hemiketal is described.     

Synthesis and coordination chemistry of organoiridium complexes supported by an anionic tridentate ligand

Treatment of deprotonated N-(dimethylaminoethyl)-2-diphenylphosphinoaniline with bis(cyclooctene)iridium chloride dimer affords a thermally stable iridium(I) olefin complex. Infrared analysis of the corresponding monocarbonyl iridium(I) compound indicates a relatively electron rich metal center. Reaction of the iridium(I) cyclooctene complex with iodomethane effects oxidation of the metal yielding a five-coordinate iridium(III) methyl iodide complex which reversibly coordinates tetrahydrofuran. X-ray crystallography confirms coordination of ether to the iridium(III) methyl iodide complex and NMR spectroscopic experiments establish an equilibrium constant of 1.66(9) M for tetrahydrofuran binding. A five-coordinate iridium(III) dimethyl complex has also been prepared and characterized by X-ray diffraction. Hydrogenolysis of the dialkyl species permits identification of a short-lived classical iridium(III) dihydride complex.     

Selective rearrangements of 4a,5-epoxides of 4,4-dimethyl-1,2,3,4,6,8a-hexahydronaphthalenes.

Epoxidation selectivity of a number of 4,4-dimethyl-1,2,3,4,6,8a-hexahydronaphthalenes 4 were examined. Exposure of the isolated α-epoxides 7provided excellent yields (79–92%) or rearranged fused indene-oxetanes 8. Treatment of β-epoxides 5 with BF3·OEt₂ also yields oxetanes 8 and related alcohols 9 and 10.