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Synlett 2014; 25(08): 1150-1154
DOI: 10.1055/s-0033-1341065
DOI: 10.1055/s-0033-1341065
letter
Allylic Substitution of Esters Derived from 2-Bromocyclohex-2-enol with Aryl Copper Reagents and Synthetic Utilization of the Derived anti SN2′ Products
Further Information
Publication History
Received: 23 January 2014
Accepted after revision: 03 March 2014
Publication Date:
03 April 2014 (online)
Abstract
Allylic substitution of esters derived from 2-bromocyclohex-2-enol with PhMgBr-based copper reagent was investigated to find high anti SN2′ selectivity with the diethyl phosphate, whereas other esters such as picolinate, acetate, and mesylate resulted in partial racemization or recovery of the starting esters. This protocol was applied to the copper reagent derived from 2-Me-4-MeOC6H3MgBr and CuBr·SMe2 and the olefin part of the anti SN2′ product was cleaved for a synthesis of patchouli alcohol.
Key words
allylic substitution - bromocyclohex-2-enol - copper - Grignard reagent - patchouli alcoholSupporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
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References and Notes
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- 16 General Procedure To an ice-cold suspension of CuBr·SMe2 (114 mg, 0.555 mmol) in THF (4 mL) was added PhMgBr (0.68 mL, 0.703 M in THF, 0.48 mmol) dropwise. The mixture was stirred at 0 °C for 30 min and cooled to –40 °C. A solution of phosphate 2E (95% ee, 49.7 mg, 0.159 mmol) in THF (4 mL) was added to the mixture dropwise. After 3 h at 0 °C the reaction was quenched by addition of sat. NH4Cl and purification of the crude product by chromatography afforded 3a (34.9 mg, 93%): 89% ee by HPLC; 94% CT. 1H NMR (400 MHz, CDCl3): δ = 1.50–1.68 (m, 2 H), 1.76–1.85 (m, 1 H), 2.09–2.27 (m, 3 H), 3.66–3.76 (m, 1 H), 6.35 (dt, J = 1, 4 Hz, 1 H), 7.21–7.27 (m, 3 H), 7.30–7.36 (m, 2 H). 13C-APT NMR (100 MHz, CDCl3): δ = 17.9 (–), 27.8 (–), 33.9 (–), 49.8 (+), 124.4 (–), 126.7 (+), 128.3 (+), 128.4 (+), 132.0 (+), 143.4 (–).
Recent syntheses: