LETTER
Spirocyclic Sulfates from Tertiary Cyclopropanols
C
(5) For examples, see: (a) Raiman, M. V.; Il’ina, N. A.;
Kulinkovich, O. G. Synlett 1999, 1053. (b) Stolle, A.;
Ollivier, J.; Piras, P. P.; Salaün, J.; de Meijere, A. J. Am.
Chem. Soc. 1992, 114, 4051. (c) Racouchot, S.; Silvestre, I.;
Ollivier, J.; Kozyrkov, Yu. Yu.; Pukin, A.; Kulinkovich, O.
G.; Salaün, J. Eur. J. Org. Chem. 2002, 2160.
(6) For examples, see: (a) Epstein, O. L.; Kulinkovich, O. G.
Tetrahedron Lett. 2001, 42, 3757. (b) Chevtchouk, T. A.;
Isakov, V. E.; Kulinkovich, O. G. Tetrahedron 1999, 55,
13205. (c) Kulinkovich, O. G.; Astashko, D. A.; Tyvorskii,
V. I.; Ilyina, N. A. Synthesis 2001, 1453. (d) Kozyrkov, Yu.
Yu.; Kulinkovich, O. G. Synlett 2002, 443. (e) Kozyrkov,
Yu. Yu.; Kulinkovich, O. G. Synlett 2004, 344.
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); 13
C
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) For reviews on the synthesis and application of
cyclopropanols, see: (a) Gibson, D. H.; DePuy, C. H. Chem.
Rev. 1974, 74, 605. (b) Kulinkovich, O. G. Chem. Rev. 2003,
103, 2597. (c) Kulinkovich, O. G. Russ. Chem. Bull. 2004,
53, 1065. (d) Wolan, A.; Six, Y. Tetrahedron 2010, 66, 15.
(e) Haym, I.; Brimble, M. A. Org. Biomol. Chem. 2012, 10,
7649. (f) Cha, J. K.; Kulinkovich, O. G. Org. React.
(Hoboken, NJ U. S.) 2012, 77, 1.
(8) (a) Esposito, A.; Taddei, M. J. Org. Chem. 2000, 65, 9245.
(b) Bekish, A. V.; Kulinkovich, O. G.; Prokhorevich, K. N.
Tetrahedron Lett. 2004, 45, 5253. (c) Bekish, A. V.;
Kozyrkov, Y. Y.; Kulinkovich, O. G.; Lysenko, I. L.;
Matiushenkov, E. A. Synthesis 2005, 1713.
(9) For reviews on asymmetric synthesis of lactone 1c, see:
(a) Manzocchi, A.; Casati, R.; Fiecchi, A.; Santaniello, E.
J. Chem. Soc., Perkin Trans. 1 1987, 2753. (b) Jacobs, H.;
Berryman, K.; Jones, J.; Gopalan, A. Synth. Commun. 1990,
20, 999. (c) Taylor, S. K.; Atkinson, R. F.; Almli, E. P.; Carr,
M. D.; Van Huis, T. J.; Whittaker, M. R. Tetrahedron:
Asymmetry 1995, 6, 157. (d) Ramachandran, P. V.; Pitre, S.;
Brown, H. C. J. Org. Chem. 2002, 67, 5315. (e) Stangeland,
E. L.; Sammakia, T. J. Org. Chem. 2004, 69, 2381.
(10) Kim, B. M.; Sharpless, K. B. Tetrahedron Lett. 1989, 30,
655.
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.
(11) The ratio of diastereomers with a chiral sulfur atom
equilibrated by boiling a solution of sulfite 4a in diethyl
ether for four hours, as determined by 1H-NMR
spectroscopy (see Supporting Information).
(12) Sulfites 4a–c were obtained by a slightly modified Sharpless
procedure using freshly distilled SOCl2 with anhyd pyridine
instead of Et3N as the base. The mixture was stirred at 0 °C
for 0.5 h (TLC). The crude products were obtained as clear
pale-yellow liquids and were used in the next step without
further purification. Samples for spectroscopic analysis were
purified by chromatography on a short column of silica gel.
(13) 7-Methyl-4,6-dioxa-5-thiaspiro[2.4]heptane 5-Oxide (4a)
Colorless liquid (7:3 mixture of two inseparable
(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.
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).
(15) (a) Wasserman, H. H.; Hearn, M. J.; Cochoy, R. E. J. Org.
Chem. 1980, 45, 2874. (b) Kuhlman, T. S.; Pittelkow, M.;
Sølling, T. I.; Møller, K. B. Angew. Chem. Int. Ed. 2013, 52,
2247.
(16) (a) Denis, J. M.; Le Perchec, P.; Conia, J. M. Tetrahedron
1977, 33, 399. (b) Nemoto, H.; Miyata, J.; Hakamata, H.;
Fukumoto, K. Tetrahedron Lett. 1995, 36, 1055.
(17) Miyata, J.; Nemoto, H.; Ihara, M. J. Org. Chem. 2000, 65,
504.
(18) (a) Salaun, J.; Garnier, B.; Conia, J. M. Tetrahedron 1974,
30, 1413. (b) Cho, S. Y.; Cha, J. K. Org. Lett. 2000, 2, 1337.
(19) (a) Shevchuk, T. A.; Kulinkovich, O. G. Zh. Org. Khim.
2000, 36, 515; Russ. J. Org. Chem. (Engl. Transl.) 2000, 36,
491. (b) Hussain, M. M.; Li, H.; Hussain, N.; Ureña, M.;
Carroll, P. J.; Walsh, P. J. J. Am. Chem. Soc. 2009, 131,
6516.
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Synlett 2014, 25, A–D