LETTER
Cross-Coupling Reaction of Allyl- and Benzylzinc with Alkenyl Sulfides
2063
1) NiCl2 (10 mol%), P(2-furyl)3 (20 mol%)
2) n-BuLi (20 mol%)
Ph
3) CH2=CHCH2ZnCl (2a), THF, 60 °C
Ph
Ph
SPh
6 (55%)
Ph
PhCH2ZnBr (2b)
Ph
NiCl2dppe (5 mol%)
5
Ph
7 (52%)
Ph
THF, 60 °C
Scheme 1 Reaction of trisubstituted alkenyl sulfide 5 with organozinc reagent
(10) (a) Metzger, A.; Scade, A. A.; Knochel, P. Org. Lett. 2008,
10, 1107. (b) Soorukram, D.; Boudet, N.; Malakhov, V.;
Knochel, P. Synthesis 2007, 3915.
Acknowledgment
This work was financially supported by the Japanese Ministry of
Education, Culture, Sports, Science and Technology and by the
Kyoto University, International Innovation Centre.
(11) Ogawa, A.; Ikeda, T.; Kimura, K.; Hirao, T. J. Am. Chem.
Soc. 1999, 121, 5108.
(12) The use of Ni(0) catalyst which was prepared from Ni(II)
and BuLi was not so effective. On the contrary Ni(II)
catalyst gave the product with a reasonable yield. In this
case, the formation of a radical species from benzylnickel
intermediate may be a possible route. In fact, the addition of
TEMPO interfered with the reaction. In the reaction of
alkenyl sulfide with arylmethylzinc bromide (entry 4 in
Table 3) addition of TEMPO (1 equiv) resulted in the low
yield of 6a (14%).
References and Notes
(1) (a) Metal-Catalyzed Cross-Coupling Reactions, 2nd ed.;
de Meijere, A.; Diederich, F., Eds.; Wiley-VCH: Weinheim,
2004. (b) Cross-Coupling Reactions: A Practical Guide, In
Topics in Current Chemistry, Vol. 219; Miyaura, N., Ed.;
Springer: Berlin, 2002, .
(2) (a) Ritter, K. Synthesis 1993, 735. (b) Negishi, E.;
Oweczarczyk, Z.; Swanson, D. R. Tetrahedron Lett. 1991,
32, 4453. (c) Dunet, G.; Knochel, P. Synlett 2006, 407.
(3) Lee, K.; Lee, J.; Lee, P. H. J. Org. Chem. 2002, 67, 8265.
(4) Stille, J. K. Angew. Chem. Int. Ed. Engl. 1986, 25, 508.
(5) (a) Treatment of (E)-1-phenylthio-2-phenylethene (1a) with
allylmagnesium bromide in the presence of nickel catalyst
(the same reaction conditions as in entry 9 in Table 1) did not
afford 3a. (b) Treatment of (E)-1-bromo-2-phenylethene
with allylzinc chloride in the presence of nickel catalyst (the
same reaction conditions as in entry 9 in Table 1) gave 3a in
63% yield.
(6) (a) Okamura, H.; Miura, M.; Takei, H. Tetrahedron Lett.
1979, 20, 43. (b) Flandanese, V.; Marchese, G.; Mascolo,
G.; Naso, F.; Ronzini, L. Tetrahedron Lett. 1988, 29, 3705.
(c) Itami, K.; Higashi, S.; Mineno, M.; Yoshida, J. Org. Lett.
2005, 7, 1219.
(7) Takagi, K.; Hayama, N.; Sasaki, K. Bull. Chem. Soc. Jpn.
1984, 57, 1887.
(13) Preparation of (E)-1-Phenyl-1,4-pentadiene (3a): To a
solution of nickel(II) chloride (0.10 mmol) and tris(2-
furyl)phosphine (0.20 mmol) in THF (0.5 mL) under argon,
n-BuLi (0.2 mmol, 1.6 M in hexane) was added and stirred
for 15 min at 25 °C. To the mixture, after a solution of (E)-
1-phenylthio-2-phenylethene (1a) in THF (1.0 mL) was
added, allylzinc chloride (2a; 2.0 mmol, 0.7 M in THF) was
added dropwise. The resulting mixture was stirred for 4 h at
60 °C. After aqueous workup, purification by silica gel
column chromatography gave (E)-1-phenyl-1,4-pentadiene
(3a) in 99% yield. 1H NMR (300 MHz, CDCl3): d = 7.17–
7.37 (m, 5 H), 6.42 (d, J = 15.9 Hz, 1 H), 6.23 (dt, J = 6.3,
15.9 Hz, 1 H), 5.90 (ddt, J = 6.3, 10.5, 15.9 Hz, 1 H), 5.05–
5.16 (m, 2 H), 2.97 (ddt, J = 1.5, 6.3, 6.3 Hz, 2 H).
Preparation of (E)-1,3-Diphenyl-1-propene (3h): To a
solution of NiCl2(dppe) (0.05 mmol) in THF (0.5 mL) under
argon, benzylzinc bromide (2.0 mmol, 0.7 M in THF) was
added dropwise, and then a solution of (E)-1-phenylthio-2-
phenylethene (1a; 1.0 mmol) in THF (1.0 mL) was added.
The resulting mixture was stirred for 4 h at 60 °C. After
aqueous workup, purification by silica gel column
chromatography gave (E)-1,3-diphenyl-1-propene in 78%
yield. 1H NMR (300 MHz, CDCl3): d = 7.17–7.38 (m, 10 H),
6.46 (d, J = 15.9 Hz, 1 H), 6.36 (dt, J = 6.3, 15.9 Hz, 1 H),
3.55 (d, J = 6.3 Hz, 2 H).
(8) Andersen, N. G.; Keay, B. A. Chem. Rev. 2001, 101, 997.
(9) (a) Onaka, N.; Goto, T.; Mukaiyama, T. Tetrahedron Lett.
1979, 20, 1483. (b) Quisenberry, K. T.; Smith, J. D.;
Voehler, M.; Stec, D. F.; Hanusa, T. P.; Brennessel, W. W.
J. Am. Chem. Soc. 2005, 127, 4376.
Synlett 2008, No. 13, 2061–2063 © Thieme Stuttgart · New York