Diene Synthesis by the Reductive Transposition of 1,2-Allenols

Abstract

Monoalkyl diazene species are versatile intermediates that have enabled many useful synthetic transformations in complex chemical environments. Herein we report the reductive transposition of 1,2-allenols for the direct synthesis of dienes through an alkene walk process.

Key words

allenol - diene - reduction - transposition - diazene

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• 10 General Procedure Diethyl azodicarboxylate (0.6 mmol, 1.2 equiv) was added dropwise to a solution of IPNBSH (7, 0.6 mmol, 1.2 equiv), Ph₃P (0.6 mmol, 1.2 equiv), and allenol 11 (0.5 mmol) at 0 °C in anhydrous THF (5 mL). After 5 min the reaction mixture was allowed to warm to room temperature. Once the allenol was fully consumed as indicated by TLC (ca. 30 min), trifluoroethanol (1.25 mL) and water (1.25 mL) were added, and the resulting solution allowed to stir for ca. 18 h until the Mitsunobu intermediate disappeared by TLC. Once complete, the reaction mixture was partitioned between pentane (35 mL) and water (35 mL). The layers were separated, and the organic layer was washed with water (2 × 35 mL), dried with MgSO₄, filtered, and concentrated in vacuo. The crude reaction mixture was purified by column chromatography on silica gel to afford the diene 12.
• 11 New Compounds Compound 22 (major isomer): IR (film): 2899, 2846, 1451, 998, 900 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 6.92 (ddd, J = 16.8, 11.5, 10.1 Hz, 1 H), 5.82 (t, J = 11.9 Hz, 1 H), 5.17–5.04 (m, 3 H), 2.01–1.96 (m, 3 H), 1.81 (d, J = 2.9 Hz, 6 H), 1.71 (d, J = 3.3 Hz, 6 H). ¹³C NMR (126 MHz, CDCl₃): δ = 142.7, 134.0, 127.5, 117.5, 43.4, 36.9, 36.8, 28.8. HRMS (EI): m/z calcd for C₁₄H₂₀ [M]⁺: 188.1565; found: 188.1571. Compound 31 (major isomer): IR (film): 3055, 3005, 2962, 2852, 1628, 1601, 1505, 1449, 1436, 1372, 1270, 1158, 1121 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.83–7.71 (m, 4 H), 7.51 (dd, J = 8.4, 1.8 Hz, 1 H), 7.49–7.41 (m, 2 H), 6.58 (d, J = 12.2 Hz, 1 H), 6.25 (d, J = 12.3 Hz, 1 H), 5.03 (dt, J = 16.2, 0.8 Hz, 2 H), 1.75 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 142.1, 135.6, 133.3, 133.3, 132.5, 129.5, 128.0, 127.9, 127.7, 127.4, 127.2, 126.1, 125.9, 117.3, 22.4. HRMS (EI): m/z calcd for C₁₅H₁₄ [M]⁺: 194.1096; found: 194.1093.