Abstract
The reaction of various allylic esters with tri(2-furyl)germane
in the presence of Pd(Ph3 P)4 affords the corresponding
allylic germanes in good yields at room temperature.
Key words
germanium - palladium - allylgermane - allylic
substitution - allylpalladium
References
1a Keinan E.
Greenspoon N.
Tetrahedron
Lett.
1982,
23:
241
1b Tsuji J.
Yamakawa T.
Kitao M.
Mandai T.
Tetrahedron Lett.
1978,
2075
1c Keinan E.
Greenspoon N.
J. Org. Chem.
1983,
48:
3545
1d Dessolin M.
Guillerez M.-G.
Thieriet N.
Guibe F.
Loffet A.
Tetrahedron
Lett.
1995,
36:
5741
2a Matsumoto H.
Yako T.
Nagashima S.
Motegi T.
Nagai Y.
J. Orgmet. Chem.
1978,
148:
97
2b Urata H.
Suzuki H.
Moro-oka Y.
Ikawa T.
Bull. Chem. Soc. Jpn.
1984,
57:
607
2c Tsuji Y.
Kajita S.
Isobe S.
Funato M.
J. Org. Chem.
1993,
58:
3607
2d Obora Y.
Tsuji Y.
Kawamura T.
J.
Am. Chem. Soc.
1993,
115:
10414
2e Obora Y.
Tsuji Y.
Kawamura T.
J.
Am. Chem. Soc.
1995,
117:
9814
2f Tsuji Y.
Funato M.
Ozawa M.
Ogiyama H.
Kajita S.
Kawamura T.
J. Org. Chem.
1996,
61:
5779
2g Obora Y.
Tsuji Y.
Kawamura T.
Organometallics
1993,
12:
2853
2h Watanabe H.
Saito M.
Sutou N.
Kishimoto K.
Inose J.
Nagai Y.
J. Organomet.
Chem.
1982,
225:
343
2i Sakurai H.
Kamiyama Y.
Nakadaira Y.
Chem.
Lett.
1975,
887
2j Tamao K.
Okazaki S.
Kumada M.
J.
Orgmet. Chem.
1978,
146:
87
2k Tsuji Y.
Obora Y.
J. Am. Chem. Soc.
1991,
113:
9368
2l Tsuji Y.
Rago RM.
Tomohiro S.
Tsuneishi H.
Organometallics
1992,
11:
2353
2m Matsumoto Y.
Ohno A.
Hayashi T.
Organometallics
1993,
12:
4051
2n Hayashi T.
Yamamoto A.
Iwata T.
Ito Y.
J. Chem. Soc., Chem. Commun.
1987,
398
3a Mitchell TN.
Amamria A.
Killing H.
Rutschow D.
J.
Orgmet. Chem.
1986,
304:
257
3b Killing H.
Mitchell TN.
Organometallics
1984,
3:
1318
3c Piers E.
Skerlj R.
J. Chem. Soc., Chem. Commun.
1986,
626
3d Tsuji Y.
Kakehi T.
J. Chem. Soc., Chem. Commun.
1992,
1000
3e Obora Y.
Tsuji Y.
Kakehi T.
Kobayashi M.
Shinkai Y.
Ebihara M.
Kawamura T.
J. Chem.
Soc., Perkin Trans 1
1995,
599
4a Ono K.
Ishizuka H.
Nakano T.
J. Orgmet. Chem.
1999,
587:
144
4b Nakano T.
Ono K.
Senda Y.
Migita T.
J. Organomet. Chem.
2001,
619:
313
5a Gevorgyan VN.
Ignatovich LM.
Lukevics E.
J. Orgmet.
Chem.
1985,
284:
C31
5b Kinoshita H.
Shinokubo H.
Oshima K.
J.
Am. Chem. Soc.
2002,
124:
4220
5c Nakamura T.
Yorimitsu H.
Shinokubo H.
Oshima K.
Bull. Chem. Soc. Jpn.
2001,
74:
747
5d Tanaka S.
Nakamura T.
Yorimitsu H.
Shinokubo H.
Oshima K.
Org.
Lett.
2000,
2:
1911
5e Kinoshita H.
Nakamura T.
Kakiya H.
Shinokubo H.
Matsubara S.
Oshima K.
Org. Lett.
2001,
3:
2521
5f Nakamura T.
Yorimitsu H.
Shinokubo H.
Oshima K.
Tetrahedron
2001,
57:
9827
5g Nakamura T.
Tanaka S.
Yorimitsu H.
Shinokubo H.
Oshima K.
C.
R. Acad. Sci. Paris, Chim.
2001,
4:
461
6a Akiyama T.
Iwai J.
Onuma Y.
Kagoshima H.
Chem. Commun.
1999,
2191
6b Akiyama T.
Suzuki M.
Chem. Commun.
1997,
2357
6c Akiyama T.
Iwai J.
Synlett
1998,
273
6d Akiyama T.
Iwai J.
Tetrahedron Lett.
1997,
38:
853
6e Mochida K.
Asami K.
J. Orgmet. Chem.
1982,
232:
13
6f Mochida K.
Miyagawa I.
Bull. Chem. Soc. Jpn.
1983,
56:
1875
6g Sano H.
Miyazaki Y.
Okawara M.
Ueno Y.
Synthesis
1986,
776
6h Light JPII.
Reidenor M.
Beard L.
Hershberger JW.
J.
Orgmet. Chem.
1987,
326:
17
6i Sugawara M.
Yoshida J.
J. Org. Chem.
2000,
65:
3135
7
Experimental Procedure :
Allyl acetate (60 mg, 0.6 mmol) and tri(2-furyl)germane (137 mg,
0.5 mmol) were added to a mixture of Pd(PPh3 )4 (29
mg, 0.025 mol) in DMF (1.5 mL). The mixture was stirred for 4.5
h at room temperature. The mixture was diluted with ether and filtered
through a short pad of silica gel. Concentration of the filtrate
and purification of the residue provided allyltri(2-furyl)germane (1 , 151 mg, 0.48 mol) in 96% yield:
IR(neat): 3115, 3080, 2976, 1634, 1549, 1454, 1362, 1205, 1150,
1101, 1005, 897, 745 cm-1 ; 1 H
NMR (CDCl3 ): δ: 2.45 (dd, J = 8.0
Hz, 0.5 Hz, 2 H), 4.93 (dd, J = 9.6
Hz, 1.2 Hz, 1 H), 5.01 (dd, J = 17.0 Hz,
1.2 Hz, 1 H), 5.93 (m, 1 H), 6.46 (m, 3 H), 6.78 (d, J = 3.3 Hz, 3 H), 7.73 (m, 3
H); 13 C NMR (CDCl3 ): δ = 20.94, 109.79,
115.53, 121.36, 132.82, 147.47, 152.68. Found: C, 57.48; H, 4.59%.
Calcd for C15 H14 O3 Ge: C, 57.22;
H, 4.48%.
8 Hydrogen of tri(2-furyl)germane is
reported to be significantly acidic, see: ref.
[5e
