1
Supporting Information
Stereoselective synthesis of highly functionalized tetrahydrocarbazoles
through a domino Michael-Henry reaction: an easy access of four
contiguous chiral centers
Pradeep Kumar Jaiswal, Soumen Biswas, Shivendra Singh, Biswarup Pathak, Shaikh M. Mobin and
Sampak Samanta
*, a
1. General information
All reactions were carried out under air and monitored by TLC using Merck 60 F
254
pre coated silica
gel plates (0.25 mm thickness) and the products were visualized by UV detection. Flash
chromatography was carried out with silica gel (200-300 mesh). FT-IR spectra were recorded on a
Bruker Tensor-27 spectrometer.
1
H and
13
C NMR spectra were recorded on a Bruker Avance (III) 400
MHz spectrometer. Data for
1
H NMR are reported as a chemical shift (δ ppm), multiplicity (s =
singlet, d = doublet, q = quartet, m = multiplet), coupling constant J (Hz), integration, and assignment,
data for
13
C are reported as a chemical shift. High resolutions mass spectral analyses (HRMS) were
carried out using ESI-TOF-MS. HPLC analysis was performed on YL-9100 HPLC, UV detection
monitored at appropriate wavelength respectively, using Chiralcel AD-H (0.46 cm x 25 cm) column.
Materials: All β-nitrostyrenes and organocatalyst either synthesized by literature known procedure or
purchased from commercial sources.
General experimental procedure for the synthesis of highly functionalized tetrahydrocarbazole
derivatives (entry 1-18, Table 2):
To a stirred mixture of methyl 3-formyl-1H-indole-2-acetates
1
(1a-b, 0.20 mmol) and β-nitrostyrenes
(2a-k, 0.25 mmol) in dry THF (1.0 mL) was added catalyst DABCO (10 mol%) at room temperature
for 6-12h (monitored by TLC). After that, THF was evaporated by rotary evaporator under reduced
pressure. The crude product was extracted with ethyl acetate, washed with water, dried over Na
2
SO
4
.
The evaporation of the solvent left the crude product which was purified by column chromatography
over silica-gel 230-400 mesh using EtOAc/hexane as eluent to furnish the pure product. All the
products were fully characterized by their corresponding spectroscopic data (IR,
1
H and
13
C NMR and
HRMS). The diastereomeric ratio was determined by
1
H NMR data of crude product and relative
configurations were assigned by their coupling constants (J) values of the corresponding vicinal H-
atoms (Figure 1).
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