Methyl 1-benzyl-5-methyl-2,4-diphenyl-1H-pyrrole-3-carboxyl-ate

In the title compound, C26H23NO2, the dihedral angles between the pyrrole ring and the two phenyl rings are 58.1 (6) and 71.5 (5)°. The mean planes of the 5-methyl­benzene ring and the carboxyl group are twisted by 89.5 (3) and 22.1 (9)°, respectively, from the pyrrole ring. In the crystal, weak C—H⋯O inter­actions lead to supra­molecular layers in the ab plane

Bruceolline D: 3,3-dimethyl-1H,4H-cyclopenta[b]indol-2(3H)-one

The title compound, C13H13NO, crystallizes with four independent molecules in the asymmetric unit. The 12-membered penta[b]indole rings are essentially planar, with maximum deviations ranging from 0.034 (4) to 0.036 (4) Å in the four unique molecules. In the crystal, weak C—H...O interactions are observed, which link the molecules into chains along [010]

Synthesis, Crystal Structures, and DFT Calculations of Three New Cyano(phenylsulfonyl)indoles and a Key Synthetic Precursor Compound

Three cyano-1-(phenylsulfonyl)indole derivatives, 3-cyano-1-(phenylsulfonyl) indole, (I), 2-cyano-1-(phenylsulfonyl)indole, (II), and 2,3-dicyano-1-(phenylsulfonyl) indole, (III), and a key synthetic precursor 1-(phenylsulfonyl)-1-(1,1-dimethylethyl) indole-3-carboxamide, (IV), have been synthesized and their structures determined by single crystal X-ray crystallography. (I), C15H10N2O2S, is orthorhombic with space group P 212121 and cell constants: a = 4.9459(3) Å, b = 10.5401(7) Å, c = 25.0813(14) Å, V = 1307.50(14) Å3 and Z = 4. (II), C15H10N2O2S, is monoclinic with space group C 2/c and cell constants: a = 18.062(2) Å, b = 11.293(2) Å, c = 15.922(3) Å, α = 90°, β = 124.49(2)°, g = 90°, V = 2676.7 Å3 and Z = 8. (III), C16H9N3O2S, is triclinic with space group P-1 and cell constants: a = 8.1986(8) Å, b = 9.6381(11) Å, c = 9.8113(5) Å, α = 95.053(6)°, β = 101.441(6)°, g = 108.071(9)°, V = 713.02(11) Å3 and Z = 2. (IV), C19H20N2O3S, is orthorhombic with space group P ccn and cell constants: a = 13.7605(8) Å, b = 27.3177(14) Å, c = 9.7584(6) Å, α = 90°, β = 90°, g =90°, V = 3668.2(4) Å3 and Z = 8. All four compounds have the same indole nitrogen phenylsulfonyl substituent and (I), (II), and (III) are nitrile derivatives. (IV) is a tert-butylamide. In the crystals, the dihedral angle between the mean planes of the indole and phenylsulfonyl groups are 85.4(2)° (I), 87.2(7)° (II), 75.1(7)° (III), and 88.6(2)° (IV), respectively. Additionally, DFT geometry-optimized molecular orbital calculations were performed and frontier molecular orbitals of each compound are displayed. Correlation between the calculated molecular orbital energies (eV) for the surfaces of the frontier molecular orbitals to the electronic excitation transitions from the absorption spectra of each compound has been proposed

What Controls Regiochemistry in 1,3-Dipolar Cycloadditions of Münchnones with Nitrostyrenes?

The distinct experimentally observed regiochemistries of the reactions between mesoionic münchnones and β-nitrostyrenes or phenylacetylene are shown by DFT/BDA/ETS-NOCV analyses of the transition states to be dominated by steric and reactant reorganization factors, rather than the orbital overlap considerations predicted by Frontier Molecular Orbital (FMO) Theory

Bruceolline J: 2-hydroxy-3,3-dimethyl-2,3-dihydrocyclopenta[b]indol-1(4H)-one

The 12-membered cyclopenta[b]indole ring system in the title compound, C13H13NO2, deviates only slightly from planarity (r.m.s. deviation = 0.051 Å). In the crystal, N—H...O and O—H...O hydrogen bonds link the molecules into sheets parallel to (100). The five-membered cyclopentanone ring is in slightly distorted envelope conformation with the C atom bearing the hydroxy substituent as the flap

A Unified Approach to <i>ent</i>-Atisane Diterpenes and Related Alkaloids: Synthesis of (−)-Methyl Atisenoate, (−)-Isoatisine, and the Hetidine Skeleton

A unified approach to <i>ent</i>-atisane diterpenes and related atisine and hetidine alkaloids has been developed from <i>ent</i>-kaurane (−)-steviol (<b>1</b>). The conversion of the <i>ent-</i>kaurane skeleton to the <i>ent-</i>atisane skeleton features a Mukaiyama peroxygenation with concomitant cleavage of the C13–C16 bond. Conversion to the atisine skeleton (<b>9</b>) features a C20-selective C–H activation using a Suárez modification of the Hofmann–Löffler–Freytag (HLF) reaction. A cascade sequence involving azomethine ylide isomerization followed by Mannich cyclization forms the C14–C20 bond in the hetidine skeleton (<b>8</b>). Finally, attempts to form the N–C6 bond of the hetisine skeleton (<b>7</b>) with a late-stage HLF reaction are discussed. The synthesis of these skeletons has enabled the completion of (−)-methyl atisenoate (<b>3</b>) and (−)-isoatisine (<b>4</b>)