Chemistry of Allylsulfones: A New Preparation of N-Diphenylmethylene-2-Vinyl-Substituted Cyclopropylamines

Abstract

A new methodology for the synthesis of N-diphenyl­methylene-2-vinyl-substituted cyclopropylamines, starting from the allylsulfone 11, is described. The starting material 11 can be ­obtained in both enantiomeric forms. The stereoselectivity of the cyclopropane formation has been studied by molecular modeling

Key words

cyclopropylamines - vinylsulfones - allylsulfones - cyclopropanes - Garner’s aldehyde

References

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16

Data for Compound 19: [α]_D ²⁰ -76.8 (c 1.45, CHCl₃). IR (film): ν_max = 3058, 2928, 1446, 1317, 1145, 1086, 801 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 1.26 (m, 1 H, 3-Hα), 1.73 (dt, 1 H, J = 8.8, 4.4 Hz, 3-Hβ), 2.20 (m, 1 H, 2-H), 3.11 (ddd, 1 H, J = 4.4, 7.2, 9.2 Hz, 1-H), 6.33 (d, 1 H, J = 15.0 Hz, 2′-H), 6.46 (dd, 1 H, J = 9.2, 14.6 Hz, 1′-H), 7.10-7.61 (m, 13 H, Ar-), 7.84 (m, 2 H, H _ortho , -SO₂Ph). ¹³C NMR (50 MHz, CDCl₃): δ = 19.8 (C-3), 26.1 (C-2), 46.3 (C-1), 127.4-129.1 (CH-Ar), 130.0 (C-2′), 133.1 (C _para , -SO₂Ph), 136.3 and 139.4 (C _ipso , -Ph), 141.0 (C _ipso , -SO₂Ph), 148.1 (C-1′), 168.7 (CPh₂). MS: m/z (%) = 388 (30) [MH⁺], 307 (15), 246 (35), 154 (100), 77 (55). HMRS: m/z calcd for C₂₄H₂₂NSO₂: 388.1371; found: 388.1321 [MH⁺].

17

The molecular modeling studies were carried out with Maestro v. 5.1.016 coupled to MacroModel v. 8.1.031, both supplied by Schrodinger, Inc. of Portland, OR, USA. Starting structures were built by sketching and were atom-typed automatically and energy-minimized using up to 5000 iterations of TNCG minimization to default convergence. The conformational search was carried out using the MCMM/Lowmode mixed method, with default settings based upon the automated setup procedure within Maestro. The conformational constraints were added manually and set to 25, 100 or 400 kJ/mol in three separate runs for each of the four models (cis- and trans-cyclopropane, and torsional constraint set to 0 or 180 degrees). The number of trials was set to 100 since at this value all the low-energy conformations were found at least 4 times. Minimizations were all achieved with up to 5000 iterations of TNCG optimization to default convergence, and all structures were successfully converged.