A Concise Total Synthesis of 2-epi-(–)-Pachastrissamine via a Three-Component Tandem Cross-Metathesis–Intramolecular S_N2′ Substitution–Cross-Metathesis Sequence

Abstract

A highly concise and efficient total synthesis of 2-epi-(–)-pachastrissamine is described utilizing a three-component tandem cross-metathesis–intramolecular S_N2′ substitution–cross-metathesis from the readily available alcohol (+)-8, wherein the substituted tetrahydrofuran formation and alkyl-chain extension are both accomplished in a one-pot manner. This route allows for direct access to pachastrissamines and their synthetic analogues at C(2).

Key words

total synthesis - tandem reaction - stereoselective synthesis - natural products - 2-epi-pachastrissamine

• References and Notes


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• 17 The spectral data of this penultimate intermediate (–)-5 proved identical in all respects to the data previously reported by Kim and co-workers^6b with the opposite optical rotation value.
• 18 Spectral Data for 2-epi-(–)-Pachastrissamine (2) [α]_D ²⁵ –9.6 (c 0.2, MeOH). ¹H NMR (500 MHz, CDCl₃): δ = 4.13 (dd, J = 8.9, 6.5 Hz, 1 H), 3.58–3.63 (m, 2 H), 3.47–3.48 (m, 1 H), 3.40 (dd, J = 8.8, 6.9 Hz, 1 H), 1.25–1.73 (m, 29 H), 0.88 (t, J = 6.8 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 85.2, 74.8, 73.2, 52.6, 33.7, 31.9, 29.68, 29.66, 29.65, 29.59, 29.55, 29.4, 25.9, 22.7, 14.1. IR (neat): 3341, 3282, 3073, 2954, 2921, 2850, 1470, 1036, 759 cm^–1. HRMS (CI): m/z calcd for C₁₉H₃₈NO₂: 300.2903; found: 300.2900 [M + H]⁺.
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