COMMUNICATIONS
Angew. Chem. Int. Ed. 1999, 38, 2027; d) T. Toru, Y. Watanabe, M.
Tsusaka, R. Gautam, K. Tazawa, M. Bakouetila, T. Yonega, Y. Ueno,
Tetrahedron Lett. 1992, 33, 4037; e) K. Mizuno, M. Ikeda, S. Toda, Y.
Otsuji, J. Am. Chem. Soc. 1988, 110, 1288.
Me3SiO
Ph
Me3SiO
Ph
a)
b)
Ph
Ph
Ph
Ph
TePh
H
(E)-5a
7
[4] H. Fischer, Chem. Rev. 2001, 101, 3581; A. Studer, Chem. Eur. J. 2001,
7, 1159.
92% (94% Z)
c)
Me3SiO
Ph
[5] D. P. Curran, E. Eichenberger, M. Collins, M. G. Roepel, G. Thoma, J.
Am. Chem. Soc. 1994, 116, 4279; J. H. Byers, G. C. Lane, J. Org. Chem.
1993, 58, 3355; D. P. Curran, K. Kim, Tetrahedron 1991, 47, 6167.
[6] a) Controlled/Living Radical Polymerization:Progress in ATRP,
NMP and RAFT (Ed.: K. Matyaszewski), ACS Symposium Series
768, American Chemical Society, Washington DC, 2000; b) K.
Matyjaszewski, J. Xia, Chem. Rev. 2001, 101, 2921; c) A. Gridnev,
S. D. Ittel, Chem. Rev. 2001, 101, 3611; d) M. Kamigaito, T. Ando, M.
Sawamoto, Chem. Rev. 2001, 101, 3689; e) C. J. Hawker, A. W.
Bosman, E. Harth, Chem. Rev. 2001, 101, 3661.
Me3SiO
Ph
CO2Et
Ph
Ph
CO2Me
CO2Me
Ph
Ph
9
8
78% (96% Z)
58% (97% Z)
Scheme 3. a) Bu3SnH
(1.2 equiv),
azobisisobutyronitrile
(AIBN)
(0.1 equiv), 808C, 1 h (no solvent); b) dimethyl fumarate (5 equiv), Bu3SnH
(2.4 equiv), AIBN (0.1 equiv), benzene, 808C, 1 h (syringe pump addition
of Bu3SnH solution over 1 h); c) ethyl 2-tributylstannylmethylacrylate
(3 equiv), AIBN (0.1 equiv), 808C, 3 h (no solvent).
[7] a) H. Miyazoe, S. Yamago, J. Yoshida, Angew. Chem. 2000, 112, 3815;
Angew. Chem. Int. Ed. 2000, 39, 3669; b) S. Yamago, H. Miyazoe, K.
Iida, J. Yoshida, Org. Lett. 2000, 2, 3671.
AIBN gave 7 in 92% yield. Because the stereochemical
isomerization of vinyl radicals takes place very rapidly,[13] the
observed high Z stereoselectivitycan be also ascribed to the
selective hydrogen atom abstraction from 4, which is stereo-
selective because of the bulky siloxyalkyl group. The vinyl
radical 4a also reacted with electron-deficient alkenes.[11]
Thus, treatment of (E)-5a with dimethyl fumarate in the
presence of tributyltin hydride afforded the corresponding
coupling product 8 (R3, R4 CO2Me; see Scheme 3) in good
yield. The coupling of (E)-5a with ethyl 2-tributylstannyl-
methylacrylate also resulted in the desired coupling product 9
in good yield. In both cases, the olefinic stereochemistry of 5a
was highlypreserved in the products.
[8] a) S. Yamago, H. Miyazoe, R. Goto, M. Hashidume, T. Sawazaki, J.
Yoshida, J. Am. Chem. Soc. 2001, 123, 3697; b) S. Yamago, H.
Miyazoe, T. Sawazaki, J. Yoshida, Tetrahedron Lett. 2000, 41, 7517;
c) S. Yamago, M. Hashidume, J. Yoshida, Chem. Lett. 2000, 1234; d) S.
Yamago, H. Miyazoe, J. Yoshida, Tetrahedron Lett. 1999, 40, 2339;
e) S. Yamago, H. Miyazoe, J. Yoshida, Tetrahedron Lett. 1999, 40,
2343; f) S. Yamago, H. Miyazoe, R. Goto, J. Yoshida, Tetrahedron Lett.
1999, 40, 2347.
[9] Addition of 0.1 equivalents of 4-oxo-TEMPO (4-oxo-2,2,6,6-tetra-
methyl-1-piperidinoxyl; radical chain inhibitor) had a marginal effect
on the formation of 5a, which indicates that anycontribution of the
chain pathwayis negligible.
[10] CCDC 176516 contains the supplementarycrystallographic data for
m.ac.uk/conts/retrieving.html (or from the Cambridge Crystallo-
graphic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK;
fax: (44)1223-336-033; or deposit@ccdc.cam.ac.uk).
In summary, we have developed a highly convergent and
stereocontrolled synthesis of silylated allyl alcohols by
domino, sequential radical-coupling reactions. Because the
coupling reaction can be carried out with a varietyof
combinations of carbonyl compounds, alkynes, and agents to
trap the vinyl radicals, this method provides a novel and
powerful strategy for the diversity-oriented synthesis of allylic
alcohols. Moreover, since the reaction does not require the
use of a solvent, it also has the advantage of being environ-
[11] a) D. L. J. Clive, G. J. Chittattu, V. Farina, W. Kiel, S. M. Menchen,
C. G. Russell, A. Singh, C. K. Wong, N. Curtis, J. Am. Chem. Soc. 1980,
¬
102, 4438; b) D. H. R. Barton, S. D. Gero, B. Quiclet-Sire, M. Samadi,
C. Vincent, Tetrahedron 1991, 47, 9383; D. H. R. Barton, M. Ramesh,
J. Am. Chem. Soc. 1990, 112, 891; c) L.-B. Han, K. Ishihara, N. Kambe,
A. Ogawa, N. Sonoda, Phosphorous, Sulfur Silicon Relat. Elements
1992, 67, 243; L.-B. Han, K. Ishihara, N. Kambe, A. Ogawa, I. Ryu, N.
Sonoda, J. Am. Chem. Soc. 1992, 114, 7591; d) D. Crich, C. Chen, J.-T.
Hwang, H. Yuan, A. Papadatos, R. I. Walter, J. Am. Chem. Soc. 1994,
116, 8937; e) L. Engman, V. Gupta, J. Org. Chem. 1997, 62, 157;
f) M. A. Lucas, C. H. Schiesser, J. Org. Chem. 1998, 63, 3032; M. A.
Lucas, C. H. Schiesser, J. Org. Chem. 1996, 61, 5754.
[14]
mentallyfriendly.
Received: December 14, 2001 [Z18386]
[12] a) A. Fiumana, K. Jones, Chem. Commun. 1999, 1761; b) K. Miura, D.
Itoh, T. Hondo, A. Hosomi, Tetrahedron Lett. 1994, 35, 9605; c) F.
Foubelo, F. Lloret, M. Yus, Tetrahedron 1994, 50, 6715; d) M. Journet,
M. Malacria, J. Org. Chem. 1992, 57, 3085; e) E. Lee, D. S. Lee,
Tetrahedron Lett. 1990, 31, 4341.
[13] C. Galli, A. Guarnieri, H. Koch, P. Mencarelli, Z. Rappoport, J. Org.
Chem. 1997, 62, 4072; see also K. Miura, K. Oshima, K. Utimoto, Bull.
Chem. Soc. Jpn. 1993, 66, 2356.
[1] Chem. Rev. 1996, 96, issue 1; specifically, L. F. Tieze, Chem. Rev. 1996,
96, 115.
[2] D. P. Curran in Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M.
Trost, I. Fleming), Pergamon, Oxford, 1991, p. 779; P. J. Parsons, C. S.
Penkett, A. J. Shell, Chem. Rev. 1996, 96, 195; M. Malacria, Chem.
Rev. 1996, 96, 289; K. K. Wang, Chem. Rev. 1996, 96, 207.
[3] a) M. P. Sibi, J. Chen, J. Am. Chem. Soc. 2001, 123, 9472; M. P. Sibi, J.
Jianguo, J. Org. Chem. 1996, 61, 6090; G. E. Keck, C. P. Kordik,
Tetrahedron Lett. 1993, 34, 6875; D. P. Curran, W. Shen, J. Zhang, T. A.
Heffner, J. Am. Chem. Soc. 1990, 112, 6738; b) I. Ryu, N. Sonoda, D. P.
Curran, Chem. Rev. 1996, 96, 177; I. Ryu, N. Sonoda, Angew. Chem.
1996, 108, 1140; Angew. Chem. Int. Ed. Engl. 1996, 35, 1050; I. Ryu, H.
Kuriyama, S. Minakata, M. Komatsu, J.-Y. Yoon, S. Kim, J. Am. Chem.
Soc. 1999, 121, 12190; I. Ryu, H. Muraoka, N. Kambe, M. Komatsu, N.
Sonoda, J. Org. Chem. 1996, 61, 6396; I. Ryu, H. Yamazaki, A. Ogawa,
N. Kambe, N. Sonoda, J. Am. Chem. Soc. 1993, 115, 1187; I. Ryu, K.
Kusano, H. Yamakai, N. Sonoda, J. Org. Chem. 1991, 56, 5004; c) A.
Ogawa, M. Doi, K. Tsuchii, T. Hirao, Tetrahedron Lett. 2001, 42, 2317;
A. Ogawa, I. Ogawa, N. Sonoda, J. Org. Chem. 2000, 65, 7682; A.
Ogawa, M. Doi, I. Ogawa, T. Hirao, Angew. Chem. 1999, 111, 140;
[14] Green Chemistry:Frontiers in Benign Chemical Syntheses and
Processes (Eds.: P. T. Anastas, T. C. Williamson), Oxford University
Press, Oxford, 1998.
Angew. Chem. Int. Ed. 2002, 41, No. 8
¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
1433-7851/02/4108-1409 $ 20.00+.50/0
1409