K. Surendra et al. / Tetrahedron Letters 47 (2006) 2133–2136
2135
Table 2. b-Cyclodextrin catalyzed allylation of dioxolanes using Zn/allyl bromide in aqueous media
a
b
Entry
Substrate (2)
Product (3)
Time (h)
8
Yield (%)
O
O
OH
a
82
O
OH
b
c
O
8
8
84
80
Br
Br
O
OH
O
Me
Me
MeO
O
OH
d
e
O
O
10
10
80
82
MeO
OH
O
O
O
O
OH
f
10
82
O
a
1
All the products were characterized by MS, H NMR, and IR spectroscopy.
Isolated yields.
b
with the known compounds.9b These reactions could be
effectively carried out at 50 °C and did not proceed in
the absence of CD. The b-cyclodextrin can also be
recovered and reused. These reactions also occur with
aliphatic acetals and dioxolanes, however, the yields
are less than satisfactory (15–20%). Here, the role of
CD appears to activate the acetal or dioxolane group
References and notes
1. (a) Yamamoto, Y.; Asao, N. Chem. Rev. 1993, 93, 2207;
b) Marshall, J. A. Chem. Rev. 1996, 96, 31.
. (a) Roush, W. R. In Comprehensive Organic Synthesis;
Trost, B. M., Fleming, I., Heathcock, C. H., Eds.;
Pergamon: Oxford, UK, 1991; Vol. 2; (b) Thomas, E. J.
Chem. Commun. 1997, 411.
. (a) Greene, T. W.; Wuts, P. G. M. Protecting Groups in
Organic Synthesis, 2nd ed.; John Wiley & Sons: New
York, 1991; (b) Robertson, J. Protecting Groups Chemis-
try; Oxford University Press: New York, 2000; (c)
Hanson, J. R. Protecting Groups in Organic Synthesis;
John Wiley & Sons: New York, 1999.
(
2
1
1
by hydrogen bonding, thereby facilitating its cleavage
3
in situ and enhancing the reactivity of the carbonyl oxy-
gen for Barbier-type allylation reaction. Hence, the rates
of CD catalyzed acetal hydrolysis and allylation reac-
tions are nearly the same as the aldehyde formed in these
reactions is simultaneously converted to the homoallylic
alcohol.
4
. (a) Jung, M. E.; Maderna, A. J. Org. Chem. 2004, 69,
7
755; (b) Yadav, J. S.; Reddy, B. V. S.; Srihari, P. Synlett
2
001, 673; (c) Zerth, H. M.; Leonard, N. M.; Mohan, R. S.
In conclusion, this work demonstrates a new, mild,
and efficient procedure for the synthesis of homoally-
lic alcohols directly from aromatic acetals and dioxol-
anes using a zinc-mediated Barbier reaction in the
presence of b-cyclodextrin as the catalyst in water as
solvent.
Org. Lett. 2003, 5, 55, and references cited therein.
. McCluskey, A.; Mayer, D. M.; Young, D. J. Tetrahedron
Lett. 1997, 38, 5217.
. (a) Organic Synthesis in Water; Grieco, P. A., Ed.; Blackei
Academic and Professional: London, 1998; (b) Li, C.-J.;
Chan, T.-H. Organic Reactions in Aqueous Media; John
Wiley & Sons: New York, 1997; (c) Lindstrom, U. M.
Chem. Rev. 2002, 102, 2751.
5
6
7
8
. Lehn, J.-M. Angew. Chem., Int. Ed. Engl. 1988, 27, 89.
. (a) Petrier, C.; Luche, J.-L. J. Org. Chem. 1985, 50, 910;
Acknowledgement
(
1
b) Petrier, C.; Einhorn, J.; Luche, J.-L. Tetrahedron Lett.
985, 26, 1449; (c) Petrier, C.; Einhorn, J.; Luche, J.-L. J.
K.S. and N.S.K. thank CSIR, New Delhi, India, for the
award of research fellowships.
Organomet. Chem. 1987, 322, 177; (d) Wilson, S. R.;
Guazzaroni, M. E. J. Org. Chem. 1989, 54, 3087; (e)
Sjoholm, R.; Rairama, R.; Ahonen, M. J. Chem. Soc.,
Chem. Commun. 1994, 1217.
Supplementary data
9
. (a) Krishnaveni, N. S.; Surendra, K.; Rao, K. R. Chem.
Commun. 2005, 669; (b) Krishnaveni, N. S.; Surendra, K.;
Kumar, V. P.; Srinivas, B.; Reddy, C. S.; Rao, K. R.
Tetrahedron Lett. 2005, 46, 4299; (c) Krishnaveni, N. S.;