An Efficient Procedure for the 1,3-Transposition of Allylic Alcohols Based on Lithium Naphthalenide Induced Reductive Elimination of Epoxy Mesylates

Abstract

An efficient protocol for the 1,3-transposition of allylic alcohols has been developed. The method is based on the pretransformation of allylic alcohols into the corresponding epoxy mesylates, followed by the reductive elimination of the resulting epoxy mesylates by using lithium naphthalenide (LN) as a reducing agent.

Key words

allylic alcohols - 1,3-transposition - epoxy mesylates - reductive elimination - lithium naphthalenide

References and Notes

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9

The stereochemistry of 1a was elucidated based on the coupling constant in the ¹H NMR spectrum.

10

Typical Procedure for the Reductive Elimination of Epoxy Mesylates: A stock solution of LN [11] in THF (0.365 M, 20.4 mL, 7.43 mmol) precooled to -25 °C was quickly added by syringe to a solution of 1a (580 mg, 2.48 mmol) in anhyd THF (5 mL) at -25 °C under a nitrogen atmosphere. The resulting dark mixture was stirred at -25 °C for 10 min, then was quenched with H₂O (10 mL) and extracted with EtOAc (2 × 20 mL). The combined extracts were washed with sat. aq NaCl (10 mL), dried with Na₂SO₄ and concentrated. Purification by chromatography on silica gel (hexane; EtOAc-hexane, 1:10) afforded 1,5,5-trimethyl-cyclohex-2-enol (2a) as a viscous oil (291 mg, 84%). IR (KBr): 3490, 1675 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 5.66 (dt, J = 1.5, 9.9 Hz, 1 H), 5.69 (d, J = 9.9 Hz, 1 H), 1.79 (dd, J = 1.5, 15.1 Hz, 1 H), 1.77 (dd, J = 1.5, 15.1 Hz, 1 H), 1.64 (d, J = 14.0 Hz, 1 H), 1.53 (d, J = 14.0 Hz, 1 H), 1.24 (s, 3 H), 1.02 (s, 3 H), 0.93 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 132.4, 126.9, 68.2, 50.4, 38.9, 31.0, 30.9, 29.8, 27.6. HRMS (EI): m/z [M]⁺ calcd for C₉H₁₆O: 140.1201; found: 140.1204.