V. A. D’yakonov et al. / Tetrahedron Letters 48 (2007) 8583–8586
8585
5
6
. Dzhemilev, U. M.; Ibragimov, A. G. Russ. Chem. Rev.
000, 69, 121–135.
. Dzhemilev, U. M.; Ibragimov, A. G. Russ. Chem. Bull.,
Int. Ed. 1998, 47, 786–794.
solution of HCl 2 (or DCl, 10–12% solution in D
The crude products 2 or 3, respectively, were extracted
2
O, 3).
2
with Et O or pentane, quenched with an 8–10% (aq)
2
solution of HCl or DCl. The layers were separated and the
7
8
. Dzhemilev, U. M. Tetrahedron 1995, 51, 4333–4346.
. Dzhemilev, U. M.; Ibragimov, A. G. J. Organomet. Chem.
2
aqueous phase was extracted with Et O or hexane. The
combined organic extracts were washed with water,
saturated aqueous NaHCO , dried (CaCl ), filtered and
1
994, 466, 1–4.
3
2
1
3
9
. Dzhemilev, U. M.; Ibragimov, A. G.; Zolotarev, A. P.;
Musluhov, R. R.; Tolstikov, G. A. Bull. Acad. Sci. USSR,
Div. Chem. Sci. 1989, 38, 194–195.
distilled. 6-Ethyl-6-aluminaspiro[3.4]octane (1). C NMR
(75 MHz, CDCl ): d 1.07, 6.61, 8.27, 14.88, 17.58, 34.32,
34.55, 38.91, 44.22. 1-Ethyl-1-methylcyclobutane (2). Bp
3
1
1
0. Dzhemilev, U. M.; Ibragimov, A. G.; Zolotarev, A. P.;
88–89 °C. H NMR (100 MHz, CDCl
J = 6.0 Hz, 3H, CH ), 1.04 (s, 3H, CH ), 1.48 (m, 2H,
CH ), 1.71 (m, 6H, CH ring); C NMR (75 MHz,
3
): d 0.81 (t,
Tolstikov, G. A. Bull. Acad. Sci. USSR, Div. Chem. Sci.
3
3
1
3
1
990, 39, 2570–2578.
2
2
1
1. Dzhemilev, U. M.; Ibragimov, A. G.; Morozov, A. B.;
Musluhov, R. R.; Tolstikov, G. A. Bull. Acad. Sci. USSR,
Div. Chem. Sci. 1991, 40, 1425–1427.
CDCl ): d 8.49, 14.84, 25.68, 32.84, 34.8, 39.1. MS (m/z,
%): 98 (27, M ), 70 (66), 69 (37), 56 (26), 55 (76), 42 (25),
3
+
41 (100). Anal. Calcd for C
7
H14: C, 85.63; H, 14.37.
1
2. Dzhemilev, U. M.; Ibragimov, A. G.; Morozov, A. B.
Mendeleev Commun. 1992, 26–28.
3. Dzhemilev, U. M.; Ibragimov, A. G.; Morozov, A. B.;
Musluhov, R. R.; Tolstikov, G. A. Bull. Russ. Acad. Sci.,
Div. Chem. Sci. 1992, 41, 1089–1093.
Found: C, 85.42; H, 14.29. Yield 92%. 1-(2-Deuterio-
1
ethyl)-1-(deuteriomethyl)cyclobutane (3).
(100 MHz, CDCl ): d 0.83 (t, J = 6.0 Hz, 2H, CH
1.02 (s, 2H, CH D), 1.45 (m, 2H, CH ), 1.76 (m, 6H, CH
NMR (75 MHz, CDCl3): 8.24 (t,
H
NMR
1
3
2
D),
2
2
2
1
3
ring);
C
d
1
4. Kondakov, D. Y.; Negishi, E. J. Am. Chem. Soc. 1996,
JCD = 19.1 Hz), 14.81, 25.37 (t, JCD = 19.05 Hz), 32.81,
34.76, 39.15. MS (m/z, %): 100 (21, M ), 72 (28), 71 (41),
+
1
18, 1577–1578.
1
5. Dzhemilev, U. M.; Ibragimov, A. G.; Khafizova, L. O.;
70 (34), 57 (30), 56 (48), 55 (20), 44 (69), 43 (27), 42 (63), 41
(64), 40 (100). Anal. Calcd for C H D : C, 83.92; H,
Rusakov, S. V.; Khalilov, L. M. Mendeleev Commun.
7
12
2
1
997, 198–199.
12.07; D, 4.01. Found: C, 83.79; H + D, 15.93. Yield 92%.
1
6. Negishi, E.; Montchamp, J.-L.; Anastasia, L.; Elizarov,
A.; Choueiry, D. Tetrahedron Lett. 1998, 39, 2503–2506.
7. Ibragimov, A. G.; Khafizova, L. O.; Satenov, E. G.;
Khalilov, L. M.; Yakovleva, L. G.; Rusakov, S. V.;
Dzhemilev, U. M. Russ. Chem. Bull., Int. Ed. 1999, 48,
30. Synthesis of spiro[3.3]heptane (4): To crude 1 at 0 °C were
2 3 2
added Et O (5 ml), Ph P (0.5 mmol), Pd(acac) (0.5 mmol)
1
and allyl chloride (30 mmol) dropwise. The reaction
mixture was allowed to warm to ꢀ20 °C and stirred for
8 h. The reaction was quenched with an 8–10% (aq)
solution of HCl. The layers were separated and the
1
574–1580.
1
1
2
2
8. Khafizova, L. O.; Ibragimov, A. G.; Gilfanova, G. N.;
Khalilov, L. M.; Dzhemilev, U. M. Russ. Chem. Bull., Int.
Ed. 2001, 50, 2188–2192.
9. Ibragimov, A. G.; Khafizova, L. O.; Gilfanova, G. N.;
Dzhemilev, U. M. Russ. Chem. Bull., Int. Ed. 2002, 51,
aqueous phase was extracted with Et O or pentane. The
combined organic extracts were washed with water,
2
saturated aqueous NaHCO
3
, dried (CaCl
2
), filtered and
1
distilled. Bp 96–97 °C. H NMR (100 MHz, CDCl ): d
3
1
3
0.92–2.54 (m, 12H, CH
CDCl ): d 16.34, 35.19, 44.21. MS, m/z: 96 (M ). Anal.
Calcd for C 12: C, 87.42; H, 12.58. Found: C, 87.21; H,
2
ring); C NMR (75 MHz,
+
2
255–2260.
3
0. Dzhemilev, U. M.; Ibragimov, A. G.; Zolotarev, A. P.;
Khalilov, L. M.; Musluhov, R. R. Bull. Russ. Acad. Sci.,
Div. Chem. Sci. 1992, 41, 300–305.
1. Dzhemilev, U. M.; Ibragimov, A. G.; Khafizova, L. O.;
Khalilov, L. M.; Vasil’ev, Yu. V.; Tuktarov, R. F.;
Tomilov, Yu. V.; Nefedov, I. M. Russ. Chem. Bull., Int.
Ed. 1999, 48, 567–569.
7
H
12.39. Yield 88%.
31. Synthesis of 6-thiaspiro[3.4]octane (5): To crude 1 at
À40 °C, thionyl chloride (30 mmol) was added dropwise,
the reaction stirred for 8 h and then treated with an 8–10%
(aq) solution of HCl. The crude was extracted with diethyl
ether or hexane and purified by distillation in vacuo. Bp
1
2
2. Dzhemilev, U. M.; Ibragimov, A. G.; Khafizova, L. O.;
Khalilov, L. M.; Vasil’ev, Yu. V.; Tomilov, Yu. V. Russ.
Chem. Bull., Int. Ed. 2001, 50, 297–299.
92–93 °C (20 Torr). H NMR (400 MHz, CDCl
3
): d 1.1–
1.23 (m, 2H, C(1)H , C(3)H ), 1.31–2.15 (m, 7H, C(1)H ,
a
a
b
C(2)H , C(3)H , C(5)H , C(8)H ), 2.21–3.24 (m, 3H,
2
b
a
2
1
3
2
2
2
2
3. Dzhemilev, U. M.; Ibragimov, A. G.; Zolotarev, A. P.
Mendeleev Commun. 1992, 135–136.
4. Negishi, E.; Kondakov, D. Y. Chem. Soc. Rev. 1996, 26,
C(5)H
b
, C(7)H
2
); C NMR (125 MHz, CDCl
3
): d 15.29,
30.60, 32.75, 40.95, 42.19, 42.64. MS (m/z, %): 128 (56,
+
M ), 100 (74), 99 (54), 85 (100), 79 (13), 72 (14), 67 (22), 65
4
17–426.
(10), 54 (11), 53 (12), 45 (18), 41 (15). Anal. Calcd for
C H12S: C, 65.56; H, 9.43; S, 25.01. Found: C, 65.34; H,
7
9.21; S, 24.89. Yield 62%.
5. Negishi, E.; Kondakov, D. Y.; Choueiry, D.; Kasai, K.;
Takahashi, T. J. Am. Chem. Soc. 1996, 118, 9577–9588.
6. Dzhemilev, U. M.; Ibragimov, A. G.; Ramazanov, I. R.;
Khalilov, L. M. Russ. Chem. Bull., Int. Ed. 1997, 46, 2150–
32. Synthesis of spiro[3.4]oct-6-yl ester formic acid (6): To
crude 1 at À15 °C were added CuCl (1 mmol) and
methylformate (30 mmol) dropwise. The reaction mixture
was allowed to warm to ꢀ20 °C and stirred for 8 h. The
reaction was quenched with an 8–10% (aq) solution of
HCl. The layers were separated and the aqueous phase
2
152.
2
2
2
7. Dzhemilev, U. M.; Ibragimov, A. G.; Ramazanov, I. R.;
Lukyanova, M. P.; Sharipova, A. Z. Russ. Chem. Bull.,
Int. Ed. 2001, 50, 484–487.
8. Dzhemilev, U. M.; Ibragimov, A. G.; Khafizova, L. O.;
Yakupova, L. R.; Khalilov, L. M. Russ. J. Org. Chem.
005, 41, 667–672.
9. Synthesis of compounds 1–3: A 50 mL glass reactor was
charged with Cp ZrCl (0.5 mmol) in dry pentane (3 mL),
was extracted with Et
extracts were washed with water and saturated aqueous
NaHCO , dried (CaCl ), filtered and concentrated in
2
O or hexane. The combined organic
2
3
2
vacuo. The products were isolated by column chromato-
graphy on silica gel (40–100 mesh grade) with hexane/
2
2
1
methylenecyclobutane (10 mmol) and AlEt3 (12 mmol)
under a dried argon atmosphere at 0 °C. The resulting
solution was raised to ambient temperature and stirred for
EtOAc = 10:1 as eluent. Bp 91–92 °C (10 Torr). H NMR
(400 MHz, CDCl
C(5)H , C(7)H
3
): d 1.35–1.71 (m, 5H, C(1)H
a
, C(3)H
a
,
,
a
a
, C(8)H
a
), 1.75–2.13 (m, 7H, C(1)H
b
4
h. The reaction was quenched with an 8–10% aqueous
C(2)H , C(3)H , C(5)H , C(7)H , C(8)H ), 4.37–4.42 (m,
2 b b b b