Synlett 2017; 28(12): 1486-1490
DOI: 10.1055/s-0036-1588769
letter
© Georg Thieme Verlag Stuttgart · New York

Intercepting the Nazarov Oxyallyl Intermediate with α-Formyl­vinyl Anion Equivalents to Access Formal Morita–Baylis–Hillman Alkylation Products

Yen-Ku Wu
,
Rongrong Lin
,
F. G. West*
Supported by: Natural Sciences and Engineering Research Council of Canada (249822)
Further Information

Publication History

Received: 01 February 2017

Accepted after revision: 08 March 2017

Publication Date:
18 April 2017 (online)


Abstract

A Lewis acid catalyzed cationic domino reaction involving sequential electrocyclization and polar addition of allenol ethers onto the resulting oxyallyl species is described. The overall sequence allows a highly stereoselective synthesis of densely substituted cyclopentanoid compounds containing α-formylvinyl functionality which is formally equivalent to products of a Morita–Baylis–Hillman alkylation process.

Supporting Information

 
  • References and Notes

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  • 15 Representative Procedures Preparation of 3h via Method A Dienone 1d (41.5 mg, 0.14 mmol) and allenol ether 2c (61.9 mg, 0.29 mmol, 2.0 equiv) were dissolved in CH2Cl2 (2 mL, 0.1 M in dienone) under argon and cooled to –78 °C (acetone/dry ice bath). TMSOTf (27.8 μL, 0.15 mmol, 1.1 equiv) was added dropwise. The reaction mixture was stirred at the same temperature for 15 min, then was quenched with sat. aq NaHCO3 (5 mL) and warmed to r.t. The aqueous layer was extracted with CH2Cl2 (2 × 10 mL), the combined organic layers were washed with brine solution (1 × 15 mL) and dried over anhydrous MgSO4. After filtration, the solvent was removed by rotary evaporation providing a crude residue that was purified by flash column chromatography (silica gel, 8:1 hexane–EtOAc) to give 29.9 mg (51%) of 3h as a colorless oil. IR (film): 3060, 3028, 2958, 1737, 1670, 1601, 1498, 1452 cm–1. 1H NMR (500 MHz, CDCl3): δ = 9.86 (s, 1 H), 7.43–7.40 (m, 3 H), 7.40–7.36 (m, 2 H), 7.33–7.28 (m, 2 H), 7.25–7.21 (m, 3 H), 7.21–7.16 (m, 2 H), 7.15–7.10 (m, 2 H), 7.06–7.02 (m, 2 H), 3.97 (d, J = 11.9 Hz, 1 H) 3.59 (app. t, J = 11.8 Hz, 1 H), 3.23 (app. p, J = 5.8 Hz, 1 H), 1.77–1.68 (m, 1 H), 1.68–1.58 (m, 1 H), 1.47–1.35 (m, 1 H), 1.29–1.17 (m, 1 H), 0.93 (s, 3 H), 0.83 (t, J = 7.3 Hz, 3 H). 13C NMR (125 MHz, CDCl3): δ = 218.6, 192.5, 149.5, 143.3, 141.9, 136.5, 133.9, 130.0, 129.3, 128.5, 128.5, 128.0, 127.8, 126.8, 126.7, 56.0, 56.0, 55.9, 48.8, 31.5, 20.1, 16.0, 14.3 [one sp2 carbon signal is missing due to peak overlap]. HRMS (EI, M+): m/z calcd for C30H30O2: 422.2246; found: 422.2253. Preparation of 3b via Method B Dienone 1b (47.8 mg, 0.148 mmol) and allenol ether 2a (41.6 mg, 0.296 mmol, 2.0 equiv) were dissolved in DCE (2 mL, 0.1 M in dienone) under argon at r.t. Sc(OTf)3 (14.5 mg, 0.029 mmol, 0.2 equiv) was added. The reaction mixture was stirred at the same temperature for 30 min then was quenched with sat. aq NaHCO3 (5 mL). The aqueous layer was extracted with CH2Cl2 (2 × 10 mL), the combined organic layers were washed with brine (1 × 15 mL) and dried over anhydrous MgSO4. After filtration, the solvent was removed by rotary evaporation providing a crude residue that was purified by flash column chromatography (silica gel, 8:1 hexane–EtOAc) to give 30.6 mg (55%) of 3b as a colorless oil. IR (film): 3034, 2958, 1739, 1689, 1612, 1583, 1514, 1463 cm–1. 1H NMR (500 MHz, CDCl3): δ = 9.60 (s, 1 H), 7.25–7.21 (m, 2 H), 6.91–6.87 (m, 2 H), 6.80–6.75 (m, 2 H), 6.74–6.70 (m, 2 H), 6.28 (s, 1 H), 6.10 (s, 1 H), 3.84 (d, J = 12.1 Hz, 1 H), 3.73 (s, 3 H), 3.72 (s, 3 H), 3.27 (app. t, J = 11.9 Hz, 1 H), 3.03 (dq, J = 11.7, 7.1 Hz, 1 H), 1.17 (d, J = 7.1 Hz, 3 H), 0.86 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 218.8, 194.0, 158.4, 158.4, 152.1, 138.3, 133.0, 130.1, 128.7, 128.4, 114.0, 113.3, 55.1, 55.1, 54.8, 53.8, 51.9, 50.7, 16.2, 13.6. HRMS (EI, M+): m/z calcd for C24H26O4: 378.1831; found: 378.1831.
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