9
70
V. E. Isakov, O. G. Kulinkovich
LETTER
References
temperature, and the mixture was stirred for an additional 30
min. After acidic work up (20 mL of 10% aq. H SO ) and
2
4
(
(
(
(
1) (a) Kulinkovich, O. G.; Sviridov, S. V.; Vasilevskii, D. A.;
extraction with ethyl acetate, organic layers were washed
with saturated NaHCO and brine, dried over MgSO and
Pritytskaya, T. S. Zh. Org. Khim. 1989, 25, 2244.
3
4
(
b) Kulinkovich, O. G.; Sviridov, S. V.; Vasilevskii, D. A.
evaporated. 2,9-Decanediol 2b (containing near 10% of 4-
methyl-2,8-nonanediol 3b by NMR and GC-MS-analysis)
Synthesis 1991, 234.
2) (a) Kulinkovich, O. G.; Savchenko, A. I.; Sviridov, S. V.;
Vasilevskii, D. A. Mendeleev Commun. 1993, 230.
(
0.61 g, 70%) was isolated by column chromatography on
silica gel (eluent: cyclohexane–ethyl acetate). After two
crystallisations (petroleum ether–benzene) 0.38 g of
crystalline 2,9-decanediol 2b was obtained: mp 32–33 °C.
(b) Epstein, O. L.; Savchenko, A. I.; Kulinkovich, O. G.
Tetrahedron Lett. 1999, 40, 5935.
3) (a) Kulinkovich, O. G.; Sviridov, S. V.; Vasilevskii, D. A.;
Savchenko, A. I. Zh. Org. Khim. 1991, 27, 294.
19
1
(
lit. mp 33 °C); H NMR (400 MHz, CDCl ): d = 1.17 (d,
3
6
3
2
9
H, J = 6.4 Hz), 1.20–1.48 (m, 12 H), 2.07 (br s, 2 H), 3.68–
.78 (m, 2 H); C NMR (100 MHz, CDCl ) d = 23.33, 25.57,
9.48, 39.18, 67.89; MS (70 eV) 29, 45 (100%), 55, 69, 81,
(
b) Kulinkovich, O. G.; Sviridov, S. V.; Vasilevskii, D. A.;
13
3
Savchenko, A. I. Zh. Org. Khim. 1991, 27, 1428.
4) (a) Kasatkin, A.; Sato, F. Tetrahedron Lett. 1995, 36, 6079.
–1
6, 112, 123, 141, 155; IR (CCl , cm ) 3600.
4
(b) Lee, J.; Kim, H.; Cha, J. K. J. Am. Chem. Soc. 1996, 119,
(
(
14) Kulinkovich, O. G.; Epstein, O. L.; Isakov, V. E.;
4198. (c) Lee, J.; Kim, Y. G.; Bae, J. G.; Cha, J. K. J. Org.
Khmel’nitskaya, E. A. Synlett 2001, 49.
Chem. 1996, 61, 4878. (d) Lee, J.; Kang, C. H.; Kim, H.;
Cha, J. K. J. Am. Chem. Soc. 1996, 119, 291.
15) Selected NMR data of the reductive coupling products: 1-[6-
13
(1-Hydroxycyclopentyl)hexyl]-1-cyclopentanol (2d):
C
(5) (a) Kulinkovich, O. G.; de Meijere, A. Chem. Rev. 2000,
NMR (100 MHz, CDCl ): d = 23.79, 24.59, 30.18, 39.64,
3
100, 2789. (b) Sato, F.; Urabe, H.; Okamoto, S. Chem. Rev.
4
1.47, 82.51. (2E, 12E)-2,12-Tetradecadiene-4,11-diol
2000, 100, 2835.
1
(2e): H NMR (400 MHz, CDCl ): d = 1.20–1.38 (m, 8 H),
3
(
(
6) Epstein, O. L.; Kulinkovich, O. G. Tetrahedron Lett. 2001,
2, 3757.
7) In some cases, diisopropoxytitanacyclopropane is more
smoothly involved in olefin-exchange reactions than 2-
1.38–1.56 (m, 4 H), 1.67 (d, 6 H, J = 6.4 Hz), 1.72 (br s, 2
4
H), 3.98 (q, 2 H, J = 6.6 Hz), 5.40–5.48 (m, 2 H), 5.56–5.68
13
(
2
m, 2 H); C NMR (100 MHz, CDCl ): d = 17.56, 25.32,
3
9.42, 37.20, 73.00, 126.52, 134.38. 2,9-Dimethyl-2,9-
decanediol (2c): H NMR (400 MHz, CDCl ): d = 1.12–1.20
m, 12 H), 1.24–1.36 (m, 4 H), 1.36–1.46 (m, 4 H), 1.50 (br
s, 2 H); C NMR (100 MHz, CDCl ): d = 24.22, 29.14,
0.09, 43.89, 70.90. 1,10-Decanediol (2g): H NMR (400
6
substituted titanacyclopropane reagents (see ref. ).
1
3
(8) (a) Gibson, D. H.; De Puy, C. H. Chem. Rev. 1974, 74, 605.
(
(
b) Kulinkovich, O. G. Chem. Rev. 2003, 103, in press.
9) (a) Savchenko, A. I.; Kulinkovich, O. G. Russ. J. Org. Chem.
Engl. Transl.) 1997, 33, 846. (b) Chevtchouk, T. A.;
Kulinkovich, O. G. Russ. J. Org. Chem. (Engl. Transl.)
000, 36, 1124.
13
3
(
1
3
(
MHz, CDCl ): d = 1.22–1.44 (m, 12 H), 1.48–1.64 (m, 4 H),
3
13
2
.05 (br s, 2 H), 3.61 (t, 4 H, J = 6.6 Hz); C NMR (100
2
MHz, CDCl ): d = 25.66, 29.31, 29.43, 32.67, 62.85. 2,11-
3
(10) (a) Kulinkovich, O. G.; Savchenko, A. I.; Shevchuk, T. A.
1
Dodecanediol (2h): H NMR (400 MHz, CDCl ): d = 1.17
3
Russ. J. Org. Chem. (Engl. Transl.) 1999, 35, 225.
(
3
2
d, 6 H, J = 6.4 Hz), 1.24–1.50 (m, 16 H), 1.94 (br s, 2 H),
(b) Chevtchouk, T. A.; Isakov, V. E.; Kulinkovich, O. G.
13
.71–3.84 (m, 2 H); C NMR (100 MHz, CDCl ): d = 23.34,
3
Tetrahedron 1999, 55, 13205.
5.65, 29.44, 29.53, 39.25, 67.95.
(11) Quan, L. G.; Kim, S.-H.; Lee, J. C.; Cha, J. K. Angew. Chem.
Int. Ed. 2002, 41, 2160.
(
16) After acidic hydrolysis of the reaction products, diols 3b and
,5-dimethyl-2,7-octanediol were obtained in 29% yield as
4
(
12) The Fe- catalyzed ‘head-to-head’ coupling of alkenes has
been disclosed recently: Small, B. L.; Marcucci, A. J.
Organometallics 2001, 20, 5738; and references therein.
13) Typical procedure: To a solution of homoallylic alcohol 1b
an nearly equimolar mixture (GC-MS).
17) Epstein, O. L.; Savchenko, A. I.; Kulinkovich, O. G. Russ.
Chem. Bull. 2000, 278.
18) Kulinkovich, O. G. Pure Appl. Chem. 2000, 72, 1715.
(19) Wright, W. G.; Warren, F. L. J. Chem. Soc., C 1967, 284.
(
(
(
(
0.86 g, 10 mmol) in Et O (15 mL) Ti(i-PrO) (1.5 mL, 5
2
4
mmol) and i-PrMgBr (20 mmol of 1.2-1.5 M solution in
Et O) were added consequently dropwise in 30 min at room
2
Synlett 2003, No. 7, 967–970 ISSN 1234-567-89 © Thieme Stuttgart · New York