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Synlett 2014; 25(13): 1855-1858
DOI: 10.1055/s-0034-1378343
DOI: 10.1055/s-0034-1378343
letter
The First Synthesis of Spirocyclic Sulfates from Tertiary Cyclopropanols and Their Reaction with Normant Homocuprates
Weitere Informationen
Publikationsverlauf
Received: 05. Mai 2014
Accepted: 26. Mai 2014
Publikationsdatum:
25. Juni 2014 (online)
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Abstract
Spirocyclic sulfates of 2- and 3-(hydroxyalkyl)cyclopropanols, obtainable through the Kulinkovich reaction from β-and γ-hydroxy carboxylic acid esters, respectively, were synthesized for the first time. The possibility of regio- and stereoselective alkylating the spirocyclic sulfates by using Normant homocuprates has been demonstrated.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
- Supporting Information
-
References
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- 13 7-Methyl-4,6-dioxa-5-thiaspiro[2.4]heptane 5-Oxide (4a) Colorless liquid (7:3 mixture of two inseparable diastereomers); Rf = 0.61 (hexane–EtOAc, 4:1); IR (neat): 1199, 3099 cm–1; 1H NMR (400 MHz, CDCl3): δ = 0.62–0.70 (m, 0.3 H), 0.79–0.93 (m, 1.3 H), 1.00–1.13 (m, 1 H), 1.19–1.32 (m, 0.7 H), 1.28 (d, J = 6.1 Hz, 2.1 H), 1.38–1.45 (m, 0.7 H), 1.41 (d, J = 6.1 Hz, 0.9 H), 4.68 (q, J = 6.1 Hz, 0.3 H), 5.04 (q, J = 6.1 Hz, 0.7 H); 13C NMR (100 MHz, CDCl3): δ = 5.32, 5.94, 8.49, 8.94, 16.10, 17.41, 67.78, 69.16, 78.28, 81.13; MS (EI): m/z (%) = 149 (0.03) [M + 1]+, 92 (80.2), 56 (100), 43 (64.4). 7-Methyl-4,6-dioxa-5-thiaspiro[2.5]octane 5-Oxide (4b) Pale-yellow liquid (single diastereomer); Rf = 0.38 (hexane–EtOAc, 4:1); IR (neat): 3092, 1230, 1180 cm–1; 1H NMR (400 MHz, CDCl3): δ = 0.68–0.81 (m, 2 H), 1.08–1.18 (m, 3 H), 1.44 (d, J = 6.1 Hz, 3 H), 2.40 (dd, J = 12.6, 12.6 Hz, 1 H), 4.72–4.80 (m, 1 H); 13C NMR (100 MHz, CDCl3): δ = 11.26, 13.02, 21.09, 38.03, 59.09, 74.05; MS (EI): m/z (%) = 163 (0.22) [M + 1]+, 120 (6.69), 56 (100), 42 (36.3). 7-Methyl-4,6-dioxa-5-thiaspiro[2.6]nonane 5-Oxide (4c)Colorless liquid (7:3 mixture of two inseparable diastereomers); Rf = 0.69 (hexane–EtOAc, 4:1); IR (neat): 1207, 3090 cm–1; 1H NMR (400 MHz, CDCl3): δ = 0.41–0.48 (m, 0.3 H), 0.53–0.60 (m, 0.7 H), 0.67–0.79 (m, 1 H), 0.88–0.95 (m, 0.3 H), 1.00–1.06 (m, 0.7 H), 1.14–1.26 (m, 1.7 H), 1.38 (d, J = 6.1 Hz, 2.1 H), 1.42 (d, J = 7.1 Hz, 0.9 H), 1.69–2.07 (m, 2.3 H), 2.25–2.34 (m, 0.3 H), 2.45–2.54 (m, 0.7 H), 4.42–4.49 (m, 0.3 H), 5.19–5.27 (m, 0.7 H); 13C NMR (100 MHz, CDCl3): δ = 10.80, 11.18, 11.29, 13.59, 22.21, 22.49, 33.65, 34.21, 35.13 (×2), 60.53, 61.71, 70.96, 73.47; MS (EI): m/z (%) = 177 (0.09) [M + 1]+, 104 (10.18), 97 (20.70), 83 (28.66), 56 (100), 41 (32.5). 7-Methyl-4,6-dioxa-5-thiaspiro[2.5]octane 5,5-Dioxide (5b) Pale-yellow liquid (crystallized in refrigerator); yield: 6.8 g; (87%); Rf = 0.34 (hexane–EtOAc, 4:1). 1H NMR (400 MHz, CDCl3): IR (neat): ν = 832, 1174, 1205, 1398, 3103 cm–1; 1H NMR (400 MHz, CDCl3): δ = 0.72–0.88 (m, 2 H), 1.08–1.15 (m, 1 H), 1.38 (dd, J = 14.6, 2.2 Hz, 1 H), 1.37–1.43 (m, 1 H), 1.47 (d, J = 6.1 Hz, 3 H), 2.55 (dd, J = 14.6, 12.6 Hz, 1 H), 5.13 (dqd, J = 12.6, 6.1, 2.2 Hz, 1 H); 13C NMR (100 MHz, CDCl3): δ = 10.32, 12.65, 20.22, 36.73, 66.95, 82.04; MS (EI): m/z (%) = 178 (0.19) [M+], 98 (4.37), 70 (11.0), 56 (100), 42 (20.6). HRMS (HESI): m/z [M + H]+ calcd for C6H11O4S: 179.0373; found: 179.0371. 7-Methyl-4,6-dioxa-5-thiaspiro[2.6]nonane 5,5-Dioxide (5c) Colorless crystals; yield: 2.5 g; (82%); mp 38–39 °C (after column chromatography); Rf = 0.45 (hexane–EtOAc, 4:1); IR (neat): 835, 1180, 1231, 1386, 3090 cm–1; 1H NMR (400 MHz, CDCl3): δ = 0.64–0.77 (m, 2 H), 1.13–1.20 (m, 1 H), 1.40 (dt, J = 15.2, 4.0 Hz, 1 H), 1.48 (d, J = 6.1 Hz, 3 H), 1.75–1.83 (m, 1 H), 1.90–1.96 (m, 1 H), 2.01–2.11 (m, 1 H), 2.58–2.67 (m, 1 H), 4.86–4.94 (m, 1 H); 13C NMR (100 MHz, CDCl3): δ = 9.73, 13.18, 21.42, 33.67, 33.87, 66.96, 82.03; MS (EI): m/z (%) = 193 (0.09) [M + 1]+, 112 (20.48), 97 (23.32), 83 (28.79), 56 (100), 41 (22.06); HRMS (HESI): m/z [M + H]+ calcd for C7H13O4S: 193.0535; found: 193.0534.
- 14 2-Methylcyclobutanone (5a) The reaction mixture was analyzed by NMR (1D TOCSY). Spectroscopic data for the residue after Vigreux column distillation of a CCl4 extract are given. Colorless liquid; IR (ССl4): 1785 cm–1; 1H NMR (400 MHz, CDCl3): δ = 1.17 (d, J = 7.2 Hz, 3 H), 1.52–1.62 (m, 1 H), 2.18–2.28 (m, 1 H), 2.88–2.98 (m, 1 H), 3.01–3.12 (m, 1 H), 3.27–3.37 (m, 1 H); 13C NMR (100 MHz, CDCl3): δ = 14.03, 18.64, 44.67, 54.91, 212.48.
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- 20 Alkylation of Tertiary Cyclopropanol Sulfates 5 with Normant Homocuprates; General Procedure A solution of the Grignard reagent prepared from Mg (0.283 g, 11.8 mmol) and RBr (11.2 mmol) in anhyd THF (12 mL) was added dropwise to a solution of sulfate 5 (2.8 mmol) and CuI (0.64 g, 3.4 mmol) in dry THF (7 mL) at –25 °C (sat. aq CaCl2/liq. N2 bath) under argon. The mixture was stirred overnight in a freezer at –25 °C, warmed to r.t., and concentrated under reduced pressure. The residue was diluted with Et2O (25 mL) and cooled to 0 °C (ice–water bath). The solution was treated with portions of 25 wt% H2SO4 (total volume 9 mL) and stirred at r.t. for 5–6 h until no cyclic sulfate was detected (TLC) and a dark-green or black precipitate formed (low-valent copper compounds). The solids were collected by filtration and washed with Et2O (2 × 5 mL). The aqueous phase was extracted with Et2O (3 × 15 mL), and the organic extracts were combined, washed with H2O (2 × 20 mL), sat. aq NaHCO3 (1 × 20 mL), and brine (1 × 20 mL) then dried (Na2SO4). The solvents were evaporated under reduced pressure and the residue was purified by column chromatography [silica gel, PE–EtOAc (20:1)]. 1-(2-Methylbutyl)cyclopropanol (7a) Colorless liquid; yield: 287 mg; (80%); Rf = 0.54 (hexane–EtOAc, 10:1); IR (neat): 3085, 3350 cm–1; 1H NMR (400 MHz, CDCl3): δ = 0.37–0.42 (m, 1 H), 0.44–0.50 (m, 1 H), 0.69–0.81 (m, 2 H), 0.89 (t, J = 7.6 Hz, 3 H), 0.98 (d, J = 7.1 Hz, 3 H), 1.13–1.28 (m, 2 H), 1.41–1.52 (m, 1 H), 1.68–1.80 (m, 3 H); 13C NMR (100 MHz, CDCl3): δ = 11.28, 13.33, 14.35, 19.56, 29.85, 32.14, 44.92, 54.44; MS (EI): m/z (%) = 128 (1.10) [M+], 99 (42.2), 72 (92.9), 57 (93.9), 43 (100), 41 (52.4). 1-(2,3-dimethylbutyl)cyclopropanol (7e) Colorless liquid; yield: 263 mg; (66%); Rf = 0.47 (hexane–EtOAc, 10:1); IR (neat): 3085, 3338, cm–1; 1H NMR (400 MHz, CDCl3): δ = 0.36–0.41 (m, 1 H), 0.46–0.51 (m, 1 H), 0.68–0.73 (m, 1 H), 0.75–0.79 (m, 1 H), 0.80 (d, J = 7.1 Hz, 3 H), 0.87 (d, J = 7.1 Hz, 3 H), 0.92 (d, J = 7.1 Hz, 3 H), 1.12 (dd, J = 14.1, 9.1 Hz, 1 H), 1.59–1.70 (m, 1 H), 1.71–1.84 (m, 3 H); 13C NMR (100 MHz, CDCl3): δ = 12.98, 14.77, 15.65, 17.83, 20.01, 32.27, 35.89, 42.13, 54.53; MS (EI): m/z (%) = 142 (0.17) [M+], 113 (3.75), 99 (21.8), 70 (71.0), 57 (26.6), 43 (100), 41 (18.0). 1-(2-Methylheptyl)cyclopropanol (7h) Colorless liquid; yield: 319 mg; (72%); Rf = 0.40 (hexane–EtOAc, 10:1); IR (neat): 3085, 3309, cm–1; 1H NMR (400 MHz, CDCl3): δ = 0.41–0.45 (m, 2 H), 0.71–0.74 (m, 2 H), 0.86 (d, J = 6.1 Hz, 3 H), 0.88 (t, J = 7.1 Hz, 3 H), 1.08–1.16 (m, 1 H), 1.20–1.63 (m, 10 H), 1.83 (br s, 1 H); 13C NMR (100 MHz, CDCl3): δ = 13.46, 13.56, 14.11, 19.68, 23.01, 29.26, 32.72, 32.95, 35.75, 36.68, 56.09; MS (EI): m/z (%) = 170 (0.09) [M+], 123 (6.58), 98 (16.2), 85 (53.7), 72 (65.1), 57 (100), 43 (90.9);
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- 28 Methyl (3R)-3-Methylheptanoate Colorless liquid; yield: 461 mg; (91%); Rf = 0.81 (hexane–EtOAc, 10:1); [α]D +3.08 (c 6.49, CHCl3); IR (neat): 1742 cm–1; 1H NMR (400 MHz, CDCl3): δ = 0.87 (t, J = 6.1 Hz, 3 H), 0.91 (d, J = 8.0 Hz, 3 H), 1.14–1.36 (m, 6 H), 1.89–1.98 (m, 1 H), 2.10 (dd, J = 13.1, 8.1 Hz, 1 H), 2.30 (dd, J = 13.1, 6.1 Hz, 1 H), 3.66 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ = 14.00, 19.73, 22.76, 29.10, 30.14, 36.40, 41.67, 51.27, 173.77.
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For reviews, see:
For examples, see:
For examples, see:
For reviews on the synthesis and application of cyclopropanols, see:
For reviews on asymmetric synthesis of lactone 1c, see:
For recent examples of homocuprates for alkylation of sulfates, see:
For the reaction of Ph2CuLi and (CH2=CH)2CuLi with sulfonates of primary and secondary alcohols, see: