2098 Bull. Chem. Soc. Jpn., 77, No. 11 (2004)
Ó 2004 The Chemical Society of Japan
Table 2. Cyanation Reactions of Aldehydes Using 2
mmol) in dry acetonitrile (3 mL) at room temperature under a ni-
trogen atmosphere, and the mixture was stirred for 30 min at the
same temperature. After filtration of the reaction mixture and
washing of 2 with dry acetonitrile under a nitrogen atmosphere,
the filtrate was concentrated under reduced pressure, and the crude
product was chromatographed on silica gel to give 1-phenyl-3-
buten-1-ol (92.3 mg, 89% yield).
Polymer catalyst 2 was recovered nearly quantitatively (ca. 60
mg) after drying under reduced pressure, and was reused accord-
ing to the above procedure.
General Procedure for Cyanation Reaction. To polymer
catalyst 2 (61.9 mg, 0.0700 mmol) was added a mixture of cyclo-
hexanecarboxaldehyde (75.8 mg, 0.676 mmol) and trimethylsilyl
cyanide (279 mg, 2.81 mmol) in dry dichloromethane (3 mL) at
room temperature, and the mixture was stirred for 20 h at the same
temperature under a nitrogen atmosphere. After filtration and
washing with dichloromethane, the filtrate was concentrated under
reduced pressure. The crude material was treated with 1 M HCl–
tetrahydrofuran (1:20 v/v) at 0 ꢀC. After the usual workup, the
crude product was chromatographed on silica gel to give 1-cyclo-
hexyl cyanohydrine (76.7 mg, 82% yield).
General Procedure for Glyoxylate–Ene Reaction. To poly-
mer catalyst 2 (63.3 mg, 0.0683 mmol) was added a mixture of
ꢀ-methylstyrene (80.7 mg, 0.683 mmol) and ethyl glyoxylate–
toluene solution (1.02 mmol/g, 3.60 g, 3.67 mmol) in dichloro-
methane (3 mL) at room temperature; the mixture was stirred
for 30 h at the same temperature under a nitrogen atmosphere.
After filtration and washing with dichloromethane, the filtrate
was concentrated under reduced pressure, and the crude product
was chromatographed on silica gel to give ethyl 2-hydroxy-4-
phenyl-4-pentenoate (105 mg, 70% yield).
2
OH
(10 mol%)
Me3SiCN
+
RCHO
CH2Cl2, r.t.
CN
R
4
Entry
1
RCHO
Yield/%a)
71
CHO
Ph
CHO
2
3
82
62
CHO
a) Isolated yield.
Table 3. Glyoxylate–Ene Reactions Using 2
R1
O
+
H
CO2C2H5
R2
R1
R2
2
OH
(10 mol%)
CO2C2H5
CH2Cl2, r.t.
5
Entry
1
Olefin
Product
Yield/%a)
OH
70
Ph
Ph
CO2C2H5
OH
CO2C2H5
OH
CO2C2H5
OH
CO2C2H5
2
3
4
69
66
60b)
References
1
H. Urabe and F. Sato, ‘‘Lewis Acids in Organic Synthe-
1
a) Isolated yield. b) E:Z = 70:30 (determined by H NMR).
sis,’’ ed by H. Yamamoto, Wiley-VCH, Weinheim (2000),
Vol. 2, pp. 653–798.
ily prepared from commercially available polystyrene-bound
ꢀ-glycol 1 and dichlorotitanium diisopropoxide under a nitro-
gen atmosphere. When we used it as an immobilized Lewis
acid catalyst, several carbon–carbon bond-forming reactions
proceeded.
2
3
T. Mukaiyama, Org. React., 28, 203 (1982).
S. J. Shuttleworth, S. M. Allin, and P. K. Sharma, Synthe-
sis, 1997, 1217; P. Hodge, Chem. Soc. Rev., 26, 417 (1997); K.
Fujita, S. Hashimoto, A. Oishi, and Y. Taguchi, Tetrahedron Lett.,
44, 3793 (2003); K. Fujita, S. Hashimoto, M. Kanakubo, A. Oishi,
and Y. Taguchi, Green Chem., 5, 549 (2003).
Experimental
4
R. Ran, D. Fu, J. Shen, and Q. Wang, J. Polym. Sci., Part
An agitation of the reaction mixture was performed on a solid-
phase organic synthesizer (Tokyo Rikakikai Co. Ltd.). Polysty-
rene-bound glycerol 1, dichlorotitanium diisopropoxide, and ethyl
glyoxylate–toluene solution were purchased from Aldrich, Tokyo
Kasei Kogyo Co. Ltd., and Fluka, respectively.
Preparation of 2. A mixture of polystyrene-bound glycerol 1
(1.38 mmol/g, crosslinked with 1% divinylbenzene, 403.6 mg,
0.557 mmol) and dichlorotitanium diisopropoxide (262 mg, 1.11
mmol) in dry dichloromethane (4 mL) was agitated with shaking
for 5 h at room temperature under a nitrogen atmosphere. After
filtration of the reaction mixture, the resin was washed with di-
chloromethane and with acetonitrile, and then dried under reduced
pressure (519 mg, pale yellow beads). IR (KBr): 3023.9, 2913.1,
1600.3, 1492.5, 1451.3, 1365.9, 1100.1, 747.9, 696.0 cmÀ1; Anal.
Found: Cl, 8.39; O, 5.63%. Calcd: Cl, 8.43; O, 5.71%.
A: Polym. Chem., 31, 2915 (1993); H. Deleuze, X. Schultze, and
D. C. Sherrington, Polymer, 39, 6109 (1998); B. P. Santora, A. O.
Larsen, and M. R. Gagne, Organometallics, 17, 3138 (1998).
5
B. Altava, M. I. Burguete, J. M. Fraile, J. I. Garcia, S. V.
Luis, J. A. Mayoral, and M. J. Vicent, Angew. Chem., Int. Ed.,
39, 1503 (2000); H. Sellner, P. B. Rheiner, and D. Seebach, Helv.
Chim. Acta, 85, 352 (2002).
6
Elemental analyses of Cl of 2: before the exposure to the
air, 8.39%; after the exposure to the air for 24 h, 8.21%; after
the exposure to the air for 60 h, 7.55% (analized after washing
with dry acetonitrile and drying).
7
In the case of using titanium(IV) chloride, which was non-
supported Lewis acid catalyst, allylation reactions proceeded
smoothly even below the room temperature: Y. Yamamoto, Acc.
Chem. Res., 20, 243 (1987).
General Procedure for Allylation Reaction. To polymer cat-
alyst 2 (61.9 mg, 0.0700 mmol) was added a mixture of benzalde-
hyde (74.2 mg, 0.700 mmol) and tetraallyltin (98.8 mg, 0.349
8
H. Minamikawa, S. Hayakawa, T. Yamada, N. Iwasawa,
and K. Narasaka, Bull. Chem. Soc. Jpn., 61, 4379 (1988).
K. Mikami and M. Shimizu, Chem. Rev., 92, 1021 (1992).
9