2000
Configuration, stereodynamics and X-ray structure of 3-substituted-2-oxofuro[2,3-b]indoles. Morales-Ríos M. S., Suárez-Castillo O. R., Joseph-Nathan P. DOI: 10.1039/A908104F
Abstract
The molecular structure of 3a-alkyl-3-cyano-2-oxofuro[2,3-b]indoles 1ad and 3a-alkyl-3-methoxycarbonyl-2-oxofuro[2,3-b]indoles 2ac has been determined by 1H NMR spectroscopy, X-ray diffraction and semiempirical (AM1) and abinitio (HF/3-21G* level) quantum chemical calculations. Considering detailed NOE measurements and the anisotropic effects of the C(3) carbonyl ester group, the preferred configurations were determined in solution. In these compounds the thermodynamic preference of the C(3) electron-attracting substituent for the endo or exo face appears to be controlled by the steric demand of the C(3a) alkyl substituent. The structurally folded furoindoles endo-2ac evidence a repulsive interaction between the sterically crowding CO2Me group and the ? system of the benzene ring. An increase in the solvent polarity significantly alters the endo?exo ratio in favor of the endo isomer. The solid-state structures of 1d and 2a demonstrate that these compounds assume configurations which differ in the spacial orientation of the C(3) substituent, with the CN group in 1d oriented to the endo face and the CO2Me group in 2a to the exo face of the molecule, in agreement with those configurations determined in CD2Cl2 solution and from theoretical calculations.
Total Syntheses of Five Indole Alkaloids from the Marine Bryozoan Flustra foliacea
Unimolecular rearrangements of ketene-O,O-acetals and fragmentations occurring in the gas phase
Synthesis of Bromoindole Alkaloids from Laurencia brongniartii
Trapping enols of esters and lactones with diazomethane
Cleavage of alkoxycarbonyl protecting groups from carbamates by t-BuNH2
Configuration, stereodynamics and crystal structure of 3-substituted-2-oxofuro[2,3-b]indoles
First Total Synthesis of ()-Flustraminol B
Transesterifications mediated by t-BuNH2
Aromatic Bromination versus Oxidation of Indolylmalonates by Bromine