A Formal Stereoselective Synthesis of (-)-Maurenone

Abstract

An efficient formal synthesis of marine polypropionate (-)-maurenone is described. Highlights of the strategy include the utilization of a desymmetrization technique and the activation of the epoxide oxygen with a silyl triflate followed by intramolecular ­hydride transfer - a novel transformation.

desymmetrization - Sharpless asymmetric epoxidation - polyketide

References and Notes

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The spectral and physical data of aldehyde 3 and ketone 4 matched in all respects with reported data (ref. 6).
Selected Physical Data
Compound 3: clear oil; R _f = 0.43 (Et₂O-hexane, 10:90); [α]_D ²⁰ +51.6 (c 1.0 CHCl₃). [6]
Compound 4: colorless oil; R _f = 0.50 (EtOAc-hexane, 10:90); [α]_D ²⁰ +30.5 (c 1.0 CHCl₃). [6]
Compound 5: colorless oil; R _f = 0.40 (EtOAc-hexane, 10:90); [α]_D ²⁰ +19.4 (c 1.0 CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 3.65 (dd, 1 H, J = 12.0, 4.5 Hz), 3.53 (dd, 1 H, J = 12.0, 8.3 Hz), 2.95 (t, 1 H, J = 6.0 Hz), 1.95 (dd, 1 H, J = 8.3, 5.3 Hz), 1.55 (m, 2 H), 1.29 (s, 3 H), 1.05 (t, 3 H, J = 7.5 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 65.6, 61.4, 61.1, 21.4, 13.9, 10.3. LC-MS: m/z = 117 [M + H]⁺.
Compound 16: colorless oil; R _f = 0.50 (EtOAc-hexane, 10:90); [α]_D ²⁰ +42.20 (c 2.0 CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 7.25 (m, 5 H), 4.40 (Abq, 2 H), 3.55 (dd, 1 H, J = 6.0, 3.0 Hz), 2.90 (m, 1 H), 2.50 (m, 2 H), 1.58 (m, 2 H), 1.30 (m, 1 H), 1.00 (m, 12 H). ¹³C NMR (75 MHz, CDCl₃): δ = 214.9, 138.9, 128.1, 127.4, 127.3, 86.6, 74.4, 48.0, 37.0, 36.9, 23.3, 16.4, 13.8, 12.1, 7.5. HRMS: m/z calcd for C₁₇H₂₆O₂Na [M + Na⁺]: 285.1820; found: 285.1823.