7938
I. Shiina, M. Hashizume / Tetrahedron 62 (2006) 7934–7939
1
3
9
2
-OH, 10-OH), 2.31 (t, J¼6.8 Hz, 2H, 2-H), 1.70–1.22 (m,
12, 13, 14-H); C NMR (C D ): d 172.9 (1), 131.4 (9 or
6 6
1
3
2H, 3, 4, 5, 6, 7, 8, 11, 12, 13, 14, 15-H); C NMR
10), 130.8 (10 or 9), 64.0 (16), 34.9 (2), 32.2 (8 or 11),
31.8 (11 or 8), 29.2 (15), 29.9, 28.8, 28.3, 28.2, 28.1, 27.2,
27.1 (4, 5, 6, 7, 12, 13, 14), 25.3 (3). HRMS: calcd for
(
(
CDC1 ): d 174.0 (1), 74.1 (9 or 10), 73.4 (10 or 9), 64.2
3
16), 34.6 (2), 32.5, 31.4, 28.6, 28.2, 28.1, 27.7, 27.6, 25.4,
+
25.0, 23.9, 23.1 (3, 4, 5, 6, 7, 8, 11, 12, 13, 14, 15); Anal.
calcd for C H O : C, 67.10; H, 10.56. Found: C, 66.97;
H, 10.54. HRMS: calcd for C H O (M+H ) 287.2222,
1
C H O (M+H ) 253.2167, found 253.2165.
16 29 2
1
6 30 4
+
6 31 4
found 287.2223.
Acknowledgements
3
.4.2. From 5; direct lactonization of threo-aleuritic acid.
We would like to express our thanks to Ms. Mari Ohno
(Dainippon Ink and Chemicals, Inc.) for elemental analysis.
This study was partially supported by a Grant-in-Aid for
Scientific Research from the Ministry of Education, Science,
Sports, and Culture, Japan.
An experimental procedure is described for the preparation
of dihydroxylactone 8 using MNBA with a catalytic amount
of DMAPO (Table 2, Entry 7). To a solution of MNBA
(
165 mg, 0.479 mmol), triethylamine (89.1 mg, 0.881
mmol), and DMAPO (11.1 mg, 0.080 mmol) in dichloro-
methane (169 mL) at room temperature was slowly added a
solution of 5 (118 mg, 0.388 mmol) in THF (40 mL) with
a mechanically driven syringe over a 12 h period. After the
reactionmixture had been stirred for 1 h at room temperature,
References and notes
1. For reviews of fragrance chemistry see: (a) Fr a´ ter, G.;
Bajgrowicz, J. A.; Kraft, P. Tetrahedron 1998, 54, 7633–
7703; (b) Kraft, P.; Bajgrowicz, J. A.; Denis, C.; Fr a´ ter, G.
Angew. Chem., Int. Ed. 2000, 39, 2980–3010.
2. For reviews of macrocyclic musk compounds see: (a) Mathur,
H. H.; Bhattacharyya, S. C. Perfum. Essent. Oil Rec. 1966,
702–715; (b) Williams, A. S. Synthesis 1999, 1707–1723.
3. For chemical synthesis of (ꢀ)-muscone (1) see: (a) Mamdapur,
V. R.; Pai, P. P.; Chakravarti, K. K.; Nayak, U. G.;
Bhattacharyya, S. C. Tetrahedron 1964, 20, 2601–2604; (b)
Branca, Q.; Fischli, A. Helv. Chim. Acta 1977, 60, 925–944;
saturated aqueous sodium hydrogencarbonate was added at
0
ꢁ
C. The mixture was extracted with dichloromethane, and
the organic layer was washed with water and brine, and dried
over sodium sulfate. After filtration of the mixture and evapo-
ration of the solvent, the crude product was purified by
thin layer chromatography to afford dihydroxylactone 8
(
92.0 mg, 83%) as a white solid.
3.5. threo-9,10-Thiocarbonyldioxyheptadecan-16-
olide (9)
(
c) Utimoto, K.; Tanaka, M.; Kitai, M.; Nozaki, H.
To a solution of dihydroxylactone 8 (80.2 mg, 0.280 mmol)
in toluene (14 mL) were added TCDI (499 mg, 2.80 mmol)
and DMAP (3.4 mg, 0.028 mmol). After the reaction mix-
Tetrahedron Lett. 1978, 2301–2304; (d) Abad, A.; Arno, M.;
Pardo, A.; Pedro, J. R.; Seoane, E. Chem. Ind. 1985, 29–30;
(e) Nelson, K. A.; Mash, E. A. J. Org. Chem. 1986, 51,
2721–2724; (f) Terunuma, D.; Motegi, M.; Tsuda, M.;
Sawada, T.; Nozawa, H.; Nohira, H. J. Org. Chem. 1987, 52,
1630–1632; (g) Xie, Z.-F.; Suemune, H.; Sakai, K. J. Chem.
Soc., Chem. Commun. 1988, 1638–1639; (h) Porter, N. A.;
Lacher, B.; Chang, V. H.-T.; Magnin, D. R. J. Am. Chem.
Soc. 1989, 111, 8309–8310; (i) Xie, Z.-F.; Sakai, K. J. Org.
Chem. 1990, 55, 820–826; (j) Tanaka, K.; Ushio, H.; Suzuki,
H. J. Chem. Soc., Chem. Commun. 1990, 795–797; (k)
Tanaka, K.; Suzuki, H. J. Chem. Soc., Chem. Commun. 1991,
101–102; (l) Tanaka, K.; Matsui, J.; Kawabata, Y.; Suzuki,
H.; Watanabe, A. J. Chem. Soc., Chem. Commun. 1991,
1632–1634; (m) Dowd, P.; Choi, S.-C. Tetrahedron Lett.
1991, 32, 565–568; (n) Ogawa, T.; Fang, C.-L.; Suemune, H.;
Sakai, K. J. Chem. Soc., Chem. Commun. 1991, 1438–1439;
ꢁ
ture had been stirred for 4 h at 130 C, it was cooled down
toroomtemperature.Themixturewasconcentratedbyevapo-
ration of the solvent and then the crude product was purified
by thin layer chromatography to afford thiocarbonate 9
ꢁ
(
1
83.8 mg, 91%) as a white solid. Mp 73–74 C; IR (KBr):
720, 1280, 1180 cm ; H NMR (CDC1 ): d 4.55–4.43
3
ꢀ1 1
(
(
1
8
2
1
m, 2H, 9-H, 10-H), 4.21–4.08 (m, 2H, 16-H), 2.42–2.25
m, 2H, 2-H), 2.10–1.21 (m, 22H, 3, 4, 5, 6, 7, 8, 11, 12,
3, 14, 15-H); C NMR (CDC1 ): d 191.4 (CS), 173.7 (1),
3
1
3
6.1 (9), 86.1 (10), 63.9 (16), 34.4 (2), 32.4, 32.1, 28.7,
8.3, 27.9, 27.9, 27.1, 25.6, 25.0, 23.6, 23.2 (3, 4, 5, 6, 7, 8,
1, 12, 13, 14, 15). Anal. calcd for C H O S: C, 62.16;
1
7 28 4
H, 8.59. Found: C, 62.05; H, 8.61. HRMS: calcd for
C H O S (M+H ) 329.1786, found 329.1791.
+
1
7 29 4
(
o) Oppolzer, W.; Radinov, R. N. J. Am. Chem. Soc. 1993,
3
.6. (9E)-Isoambrettolide (4)
115, 1593–1594; (p) Tanaka, K.; Matsui, J.; Somemiya, K.;
Suzuki, H. Synlett 1994, 351–352; (q) (Enantiomorph)
Yamaguchi, M.; Shiraishi, T.; Hirama, M. J. Org. Chem.
1996, 61, 3520–3530; (r) Kamat, V. P.; Hagiwara, H.; Suzuki,
T.; Ando, M. J. Chem. Soc., Perkin Trans. 1 1998, 2253–
2254; (s) Matsumura, Y.; Fukawa, H.; Terao, Y. Chem.
Pharm. Bull. 1998, 46, 1484–1485; (t) Alexakis, A.;
Benhaim, C.; Fournioux, X.; Heuvel, A.; Leveque, J.-M.;
March, S.; Rosset, S. Synlett 1999, 1811–1813; (u) Louie, J.;
Bielawski, C. W.; Grubbs, R. H. J. Am. Chem. Soc. 2001,
123, 11312–11313; (v) Fujimoto, S.; Yoshikawa, K.; Itoh, M.;
Kitahara, T. Biosci. Biotechnol. Biochem. 2002, 66, 1389–
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Itoh, T.; Yamamoto, M.; Mitarai, K.; Nishii, Y. Tetrahedron
2002, 58, 8269–8280; (x) Yamamoto, T.; Ogura, M.;
To thiocarbonate 9 (20.4 mg, 0.062 mmol) was added tri-
methyl phosphite (3 mL) at room temperature. After the
reaction mixture had been stirred for 25 h at 140 C, it
was cooled down to room temperature. The mixture was con-
centrated by evaporation of the solvent and then the crude
product was purified by thin layer chromatography to afford
ꢁ
(9E)-isoambrettolide (4) (13.7 mg, 87%) as a colorless oil.
IR (neat): 1730 cm ; H NMR (C D ): d 5.42 (dddd,
ꢀ
1
1
6
6
J¼15.4, 9.5, 3.5, 1.6 Hz, 1H, 9-H or 10-H), 5.32 (dddd,
J¼15.4, 9.5, 3.8, 1.6 Hz, 1H, 10-H or 9-H), 4.08
(
2
1
t, J¼5.4 Hz, 2H, 16-H), 2.19 (t, J¼7.0 Hz, 2H, 2-H),
.12–1.97 (m, 4H, 8-H, 11-H), 1.62–1.50 (m, 2H, 3-H),
.48–1.34 (m, 2H, 15-H), 1.42–1.13 (m, 14H, 4, 5, 6, 7,