A Convenient Access to Novel Amino-Hydroxy-Methyl Stereo­triads Containing an E-Trisubstituted Vinyl Iodide Unit

Abstract

Conversion of α-amino aldehydes into protected amino-hydroxy-methyl stereotriads carrying an E-trisubstituted vinyl iodide unit was effected by means of a three-step protocol: a Marshall reaction of the α-amino aldehyde with a chiral propargylic mesylate, a silylcupration of the corresponding homopropargylic alcohol and an iododesilylation reaction of the resulting vinylsilane. This sequence delivered the expected compounds as their oxazolidinone derivatives, providing a convenient diastereoselective access to useful building blocks for polypropionate synthesis and polyketide derivatives.

Key words

alkynes - vinyl iodide - Marshall reaction - amino alcohols - ­silylcupration

• References and Notes

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• 10 General Procedure for the Synthesis of Compounds 1 from Aldehydes 4: To a suspension of Pd(OAc)₂ (24 mg, 0.107 mmol, 0.05 equiv) in THF (29 mL) at –78 °C were added Ph₃P (28 mg, 0.107 mmol, 0.05 equiv) followed by a solution of (S)-pent-3-yn-2-yl methanesulfonate 3 (866 mg, 5.35 mmol, 2.5 equiv) in THF (14 mL) and a solution of the aldehyde 4 (2.14 mmol, 1 equiv) in THF (11 mL). A solution of Et₂Zn (6.85 mL, 1 M in hexane, 6.85 mmol, 3.2 equiv) was then added over 2 h using a syringe pump. The resulting solution was allowed to warm to 0 °C, and stirred at this temperature for 2.5 h, then poured into a rapidly stirred mixture of Et₂O, sat. NH₄Cl and ice. The Et₂O layer was separated, washed with sat. NH₄Cl, dried (MgSO₄), filtered and concentrated to give a brown oil. Purification of this residue by flash chromatography afforded 2. PhMe₂SiLi (0.9 M solution in THF, 26.9 mL, 24.2 mmol, 20 equiv, prepared according to the method reported by Fleming et al.; see refs 8a and 8b) was added to a solution of CuCN (1.08 g, 12.1 mmol, 10 equiv) in THF (28 mL) at 0 °C. The reaction mixture was stirred for 1 h, then a solution of 2 (1.21 mmol, 1 equiv) in Et₂O (40 mL) was added at –78 °C. After 90 min at –78 °C, the reaction mixture was allowed to warm to r.t. over 3.5 h and quenched with sat. NH₄Cl–NH₄OH (100 mL, 9:1). The biphasic mixture was warmed to r.t. (until a dark blue aqueous solution formed) and the aqueous layer was extracted with EtOAc. The combined organic layers were washed with sat. NaHCO₃ then brine, dried (MgSO₄), filtered and concentrated. The residue was purified by flash chromatography to afford 5. To a solution of 5 (1 mmol, 1 equiv) and 2,6-lutidine (95 μL, 0.8 mmol, 0.8 equiv) in hexafluoroisopropanol (10 mL) was added at 0 °C N-iodosuccinimide (360 mg, 1.6 mmol, 2 equiv). The reaction was stirred for 1.5 h at 0 °C then a mixture of EtOAc–H₂O (1:1) was added. The aqueous phase was extracted with EtOAc (3 × 30 mL). The combined organic phases were washed with sat. Na₂S₂O₃ (30 mL), 1 M HCl (30 mL) and brine, dried (MgSO₄), filtered and concentrated. The residue was purified by flash chromatography to afford 1. Compound 1a: R_f 0.19 (cyclohexane–EtOAc, 1:1); [α]_D ²⁰ +17.6 (c = 0.93, CHCl₃). ¹H NMR (300 MHz, C₆D₆): δ = 7.16 (s, 1 H), 6.02 (dd, J = 9.4, 1.5 Hz, 1 H), 3.59 (dd, J = 8.9, 6.8 Hz, 1 H), 3.10 (quint, J = 6.5 Hz, 1 H), 2.26 (ddq, J = 9.3, 9.1, 6.7 Hz, 1 H), 2.10 (d, J = 1.6 Hz, 3 H), 0.72 (d, J = 6.4 Hz, 3 H), 0.39 (d, J = 6.7 Hz, 3 H). ¹³C NMR (75 MHz, C₆D₆): δ = 160.5, 142.2, 95.8, 82.5, 51.0, 35.1, 28.3, 16.5, 15.5. MS (CI, NH₃): m/z = 313 [M⁺ + NH₄]. Compound 1h′: R_f 0.32 (petroleum ether–EtOAc, 7:3); [α]_D ²⁰ –72.3 (c = 1.04, CHCl₃). ¹H NMR (300 MHz, C₆D₆): δ = 7.82 (s, 1 H), 5.98 (dd, J = 9.8, 1.9 Hz, 1 H), 3.67 (dd, J = 5.8, 3.7 Hz, 1 H), 2.88 (dd, J = 5.8, 3.7 Hz, 1 H), 2.24 (qd, J = 9.9, 6.8 Hz, 1 H), 2.07 (s, 3 H), 1.16–1.29 (m, 1 H), 1.01–1.14 (m, 1 H), 0.78–0.93 (m, 1 H), 0.71 (t, J = 7.2 Hz, 3 H), 0.65 (d, J = 7.5 Hz, 3 H), 0.60 (d, J = 6.7 Hz, 3 H). ¹³C NMR (75 MHz, C₆D₆): δ = 160.5, 140.9, 96.9, 81.7, 59.8, 40.0, 39.6, 28.4, 24.8, 15.4, 14.2, 11.7. MS (CI, NH₃): m/z = 355 [M⁺ + NH₄].
• 11 Crystallographic data for compounds 1a and 1h′ have been deposited with the accession numbers CCDC 1411733 and CCDC 1411732, respectively, and can be obtained free of charge from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: [phone]; E-mail: [e-mail]; Web site: www.ccdc.cam.ac.uk/conts/ retrieving.html.
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