LETTER
A Novel Annelation Methodology
1035
(
3) For the use of sulfone-containing orthoesters as annelating
agents, see: (a) De Lombaert, S.; Nemery, I.; Roekens, B.;
Carretero, J.C.; Kimmel, T.; Ghosez, L. Tetrahedron Lett.
Table 3 Deprotective-Dehydration of Bicyclic Alkanols 6
Entry
Substrates
Product
Yield(a)
1
986, 27, 5099-5102. (b) Huart, C.; Ghosez, L. Angew. Chem.
OH
H
Int. Ed. Engl. 1997, 36, 634-636. For the use of related acetals,
see: (a) Lee, T.V.; Richardson, K.A. Tetrahedron Lett. 1985,
26, 3629-3632. (b) Lee, T.V.; Boucher, R.J.; Porter, J.R.;
Taylor, D.A. Tetrahedron 1988, 44, 4233-4242.
1
92%
O
O
O
(4) (a) Pinner, A. Ber. Dtsch. Chem. Ges. 1883, 16, 325. (b) De
Wolf, R.H. Synthesis 1974, 153-172. (c) Casy, G.; Furber, M.;
Richardson, K.A.; Stephenson, G.; Taylor, R.J.K.
OH
H
Tetrahedron 1986, 42, 5849-5856. (d) Kantlehner, W. in
Comprehensive Organic Synthesis, Trost, B.M.; Fleming, I.
Eds,; Pergamon: Oxford, 1991; Vol 6, p556-599.
2
3
4
90%
99%
95%
O
O
O
(
5) Newman, M.S.; Closson, R.D. J. Am. Chem. Soc. 1944, 66,
553.
6) (a) Murata, S.; Suzuki, M.; Noyori, R. Tetrahedron 1988, 44,
259-4275. (b) Basile, T.; Longobardo, L.; Tagliavini, E.;
OH
1
(
H
4
Trombini, C.; Umani-Ronchi, A. J. Chem. Soc., Chem.
Commun. 1990, 759-760. (c) Basile, T.; Longobardo, L.;
Tagliavini, E.; Trombini, C.; Umani-Ronchi, A. J. Chem.
Soc., Chem. Commun. 1991, 391-392. (d) Longobardo, L.;
Mobbili, G.; Tagliavini, E.; Trombini, C.; Umani-Ronchi, A.
Tetrahedron 1992, 48, 1299-1316.
O
O
O
OH
H
O
O
(7) (a) Akgün, E.; Pindur, U. Synthesis 1984, 227-228. (b) Pindur,
U.; Muller, J.; Flo, C.; Witzel, H. Chem. Soc. Rev. 1987, 16,
O
75-87.
OH
(
8) (a) House, H.O.; Riehl, J.-J.; Pitt, C.G. J. Org. Chem. 1965,
30, 650-653. (b) Blomberg, C.; Hartog, F.A. Synthesis 1977,
H
5
99%(b)
18-30. (c) Walborsky, H.M.; Banks, R.B. Bull. Soc. Chim.
O
O
O
Belg. 1980, 89, 849-868. (d) Luche, J.-L.; Damiano, J.-C.
J. Am. CHem. Soc. 1980, 102, 7926-7927. (e) Molle, G.;
Bauer, P. J. Am. Chem. Soc. 1982, 104, 3481-3487.
(
a) All yields refer to pure, isolated products. The deprotective
(
f) Crandall, J.K.; Magaha, S. J. Org. Chem. 1982, 47, 5368.
dehydrations were performed by refluxing the hydroxyketals in
acetone in the presence of 5 mol% PTSA. (b) The
deprotection was realised using 3 mol% CAN in MeCN/borate
buffer pH=8 followed by gentle heating in benzene in the
presence of 5 mol% PTSA. The yield reported is for the
overall process.
(
9) (a) Kagan, H.B.; Namy, J.L. Tetrahedron 1986, 42, 6573. (b)
Molander, G.A. Chem. Rev. 1992, 92, 29-68. (c) Krief, A.;
Laval, A.-M. Chem. Rev. 1999, 99, 745-777.
(
10) The large excess of SmI required probably reflects the
2
chelation of the lanthanide reagent by the dioxolane
substituent.
(
(
(
11) This selectivity could be attributed to the large steric bulk of
the organosamarium reagent. See also references 9a-9c.
12) In the case of the hydrindane derivative, the cis-ring junction
is thermodynamically preferred.
13) The stereochemistry of several bicyclic alcohols was
unambiguously established by X-ray crystallographic analysis
either of the ketal-containing bicycle (Table 2, Entry 4) or of
the corresponding hydroxyketone obtained by CAN-catalysed
deprotection (Table 2, Entries 2 and 5). The stereochemistry
of the other bicyclic derivatives was established by
spectroscopic correlation. Tinant, B.; Feneau-Dupont, J.;
Declercq, J.-P.; Ates, A.; Markó, I.E. Bull. Soc. Chim. Belg.
Acknowledgement
Financial support of this work by the Université catholique de Lou-
vain, the Fond de la Recherche pour l'Industrie et l'Agriculture
(FRIA) as a studentship to AA, the Actions de recherche concertées
(convention 96/01-197) and Merck is highly appreciated. IEM is
grateful to Merck for receiving the Merck Young Investigator
Award.
1
997, 106, 297.
References and Notes
(
14) Typical Experimental Procedure. Preparation of 1-oxo-
(1) See for example: (a) Jung, M.E. Tetrahedron 1976, 32, 3-31.
bicyclo [4,3,0] non-4,9-ene (Table 3, Entry 1).
1-Trimethylsilyloxypentene (6g, 38.4 mmol) was dissolved in
100 mL of CH Cl containing 13.2 g (46.2 mmol) of
(b) Trost, B.M. Angew. Chem.Int. Ed., Engl. 1986, 25, 1.
(c) Denmark, S.E.; Habermas, K.L.; Hite, G.A.; Jones, T.K.
2
2
Tetrahedron 1986, 42, 2821-2829. (d) Houben-Weyl,
Methoden der Organischen Chemie, Kohlenwasserstoff-
Verbindungen, III, 997-1139.
orthoester 4 and 3.7 g (27.1 mmol) of ZnCl were added. The
2
resulting solution was stirred at 20 °C during 2.5 hrs. The
reaction mixture was washed with 35 mL of saturated
Na CO , dried over MgSO and the solvent was removed in
(
2) (a) Jones, N.; Taylor, H.T. J. Chem. Soc. 1959, 4017.
2
3
4
(b) Baddeley, G.; Taylor, H.T.; Pickles, W. J. Chem. Soc.
vacuo to afford the crude product as a yellow oil. Purification
by silicagel column chromatography (petroleum ether:ethyl
1953, 124. (c) Leriverend, P.; Conia, J.-M. Bull. Soc. Chim.
Fr. 1970, 3, 1040. (d) Weller, T.; Seebach, D. Helv. Chim.
Acta 1981, 64, 736. (e) Bal, S.A.; Marfat, A.; Helquist, P.
J. Org. Chem. 1982, 47, 5045. (f) Miyao, Y.; Tanaka, M.;
Suemune, H.; Sakai, K. J. Chem. Soc., Chem. Commun. 1989,
acetate = 3:1; R = 0.37) provided the desired adduct (10.6 g,
f
-
1 1
85%). IR (neat) n :2963, 2884, 1737 cm . H NMR (CDCl ,
3
300 MHz) d :1.6-2.3 (m, 10H), 2.51 (t, J = 8.5 Hz, 1H), 3.12-
1
3
3.30 (m, 2H), 3.9-4.1 (m, 4H). C NMR (CDCl , 75.5 MHz)
3
1535. (g) Piers, E.; Boulet, S.L. Synlett. 1998, 516.
Synlett 1999, No. 07, 1033–1036 ISSN 0936-5214 © Thieme Stuttgart · New York