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Synlett 2019; 30(18): 2073-2076
DOI: 10.1055/s-0039-1690692
DOI: 10.1055/s-0039-1690692
letter
Diene Synthesis by the Reductive Transposition of 1,2-Allenols
This work was supported by the National Science Foundation (CHE1361173). V.J.M. is a 2015 Barry M. Goldwater Scholar and gratefully acknowledges support from Northwestern University in the form of an Undergraduate Research Grant. We thank the ARCS Foundation for the Daniel D. and Ada L. Rice Foundation Scholarship to A.B.D.Further Information
Publication History
Received: 12 August 2019
Accepted after revision: 11 September 2019
Publication Date:
24 September 2019 (online)
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.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1690692.
- Supporting Information
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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.
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