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

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.

Key words

chiral phosphoric acid - chiral calcium phosphate - haloamination - enecarbamate - intermolecular difunctionalization - organocatalysis

• References and Notes


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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.