Synlett 2016; 27(04): 559-563
DOI: 10.1055/s-0035-1650585
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© Georg Thieme Verlag Stuttgart · New York

Highly Enantioselective Intermolecular Iodo- and Chloroamination of Enecarbamates Catalyzed by Chiral Phosphoric Acids or Calcium Phosphate Salts

Clément Lebée
Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Univ. Paris-Sud, Univ. Paris-Saclay, 1, av. de la Terrasse, 91198 Gif-sur-Yvette Cedex, France   Email: geraldine.masson@cnrs.fr
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Florent Blanchard
Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Univ. Paris-Sud, Univ. Paris-Saclay, 1, av. de la Terrasse, 91198 Gif-sur-Yvette Cedex, France   Email: geraldine.masson@cnrs.fr
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Géraldine Masson*
Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Univ. Paris-Sud, Univ. Paris-Saclay, 1, av. de la Terrasse, 91198 Gif-sur-Yvette Cedex, France   Email: geraldine.masson@cnrs.fr
› Author Affiliations
Further Information

Publication History

Received: 21 August 2015

Accepted after revision: 09 October 2015

Publication Date:
09 November 2015 (online)

Abstract

Highly enantio- and diastereoselective vicinal chloro- and iodoamination reaction of enecarbamates catalyzed by chiral phosphoric acids or chiral calcium organophosphates are reported. The approach described herein provides efficient access to cis-chloro and cis-iodoaminals in good yields and excellent enantioselectivities (up to 99% ee). The resulting products are converted readily into highly important trans-azidoaminals.

Supporting Information

 
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  • 18 Representative Procedure for Iodoamination Reaction A flame-dried test tube, flushed with argon, was charged with enecarbamate 1a (38.2 mg, 0.2 mmol, 2.0 equiv) and catalyst 4a (3.8 mg, 0.005 mmol, 5 mol%) sequentially and dissolved in distilled toluene (0.4 mL). The reaction mixture is stirred at r.t. for 2 min before the addition of solid NIS (2b; 22.5 mg, 0.1 mmol, 1.0 equiv) and distilled toluene (0.6 mL). The resultant reaction mixture was stirred for 2 h at r.t. Then, the reaction mixture was directly purified by flash chromatography on silica gel (n-heptane–EtOAc = 7:3) to afford the corresponding pure iodoaminal 6a as a white solid (33 mg, isolated yield 78%); dr > 95:5; [α]D 23 –45.6 (c 0.9, CHCl3); mp 172–174 °C. 1H NMR (300 MHz, CDCl3): δ = 7.37–7.32 (m, 5 H), 6.00–5.92 (m, 2 H), 5.16–5.07 (m, 2 H), 4.74–4.63 (m, 1 H), 2.70 (s, 4 H), 1.96 (d, J = 6.9 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 176.3 (2 C), 154.9, 135.9, 128.8 (2 C), 128.6 (2 C), 128.5, 67.8, 64.6, 28.1 (2 C), 24.8, 23.3 ppm. IR (neat): ν = 2925, 1703, 1513, 1455, 1382, 1258, 1012, 793 cm–1. ESI-HRMS (positive): m/z calcd for C15H17IN2O4Na [M + Na]+: 439.0125; found: 439.0128. The ee is 99% determined by HPLC (AD-H, heptane–EtOH = 80:20, flow rate = 1.0 mL/min, 254 nm): t R (minor isomer) = 10.7 min; t R (major isomer) = 13.3 min.