Table 1 Reactions of dienes with ArSSAr initiated by electro-
chemically generated ArS(ArSSAr)+
Notes and references
1 P. Metzner and A. Thuillier, Sulfur Reagents in Organic Synthesis,
Academic Press, London, 1994.
Method Aa
Yield (%)c
Method Bb
Yield (%)c
2 (a) M. C. Caserio, C. L. Fisher and J. K. Kim, J. Org. Chem., 1985,
50, 4390; (b) S. Usugi, H. Yorimitsu, H. Shinokubo and
K. Oshima, Org. Lett., 2004, 6, 601; (c) T. Kitamura,
J. Matsuyuki and H. Taniguchi, J. Chem. Soc., Perkin Trans. 1,
1991, 1607. See also; transition metal-catalyzed reactions:
(d) H. Kuniyasu, A. Ogawa, S. Miyazaki, I. Ryu, N. Kambe and
N. Sonoda, J. Am. Chem. Soc., 1991, 113, 9796; (e) A. Ogawa,
H. Kuniyasu, N. Sonoda and T. Hirao, J. Org. Chem., 1997, 62,
8361; radical addition: (f) E. I. Heiba and R. M. Dessau, J. Org.
Chem., 1967, 32, 3837; (g) L. Benati, P. C. Montevecchi and
P. Spagnolo, J. Chem. Soc., Perkin Trans. 1, 1991, 2103.
3 (a) A. J. Fry, Electroorganic Chemistry, Wiley, New York, 2nd edn,
1989; (b) K. D. Moeller, Tetrahedron, 2000, 56, 9527; (c) Organic
Electrochemistry, ed. H. Lund and O. Hammerich, Dekker,
New York, 2nd edn, 2001; (d) Electroorganic Synthesis,
ed. R. D. Little and N. L. Weinberg, Dekker, New York, 1991;
(e) J. B. Sperry and D. L. Wright, Chem. Soc. Rev., 2006, 35, 605;
(f) J. Yoshida, K. Kataoka, R. Horcajada and A. Nagaki, Chem.
Rev., 2008, 108, 2265.
Diene
Product
a: Ar0 = Ph
(Z:E = 1.4:1)
b: Ar0 = Ph (E)
77
(dr = 1.1 : 1)
82
(dr = 1 : 1)
85
(dr = 1.1 : 1)
91
(dr = 1.2 : 1)
84
(dr = 2.2 : 1)
82
(dr = 1.1 : 1)
c: Ar0 = p-MeC6H4
(Z:E = 1.2:1)
83
(dr = 1.1 : 1)
87
(dr = 1.1 : 1)
74
(dr = 2.2 : 1)
d: Ar0 = p-CIC6H4
(Z:E = 2.2:1)
e: Ar0 = o-MeC6H4
(Z:E = 1.3:1)
58
(dr = 12.1 : 1.8 : 1)
33
(dr = 10.7 : 1.5 : 1)
4 Chemical generation: (a) W. A. Smit, M. Z. Krimer and
E. A. Vorobieva, Tetrahedron Lett., 1975, 16, 2451;
(b) G. Capozzi, V. Lucchini, G. Modena and F. Rivetti, J. Chem.
Soc., Perkin Trans. 2, 1975, 361; (c) A. S. Gybin, W. A. Smit,
V. S. Bogdanov, M. Z. Krimer and J. B. Kalyan, Tetrahedron Lett.,
1980, 21, 383; (d) V. S. Bogdanov, A. S. Gybin, E. G. Cherepanova
and W. A. Smit, Izv. Akad. Nauk SSSR, Ser. Khim., 1981, 2681.
Electrochemical generation: (e) A. Bewick, D. E. Coe, J. M. Mellor
and D. J. Walton, J. Chem. Soc., Chem. Commun., 1980, 51;
(f) Q. T. Do, D. Elothmani, J. Simonet and G. L. Guillanton,
Electrochim. Acta, 2005, 50, 4792, and references therein.
5 (a) M. P. Doyle, D. J. DeBruyn and D. J. Scholten, J. Org. Chem.,
1973, 38, 625. Kennedy and Smith’s INIFER (INIFER = initiator
transfer) method is also recognized as a cation chain reaction; for
example: (b) J. P. Kennedy and R. A. Smith, J. Polym. Sci., Polym.
Chem. Ed., 1980, 18, 1523; (c) H. Mayr and C. Schade, Macromol.
Rapid Commun., 1988, 9, 483.
77
72
84d
(dr = 11.5 : 1.1 : 1) (dr = 13.8 : 2.6 : 1)
56d,e
a
Initiation method A: ArSSAr (Ar = p-MeOC6H4; 1.00 mmol) was
electrolyzed in 0.1 M Bu4NB(C6F5)4–CH2Cl2 (8 mL) at ꢀ78 1C by
using 0.06 F molꢀ1 of electricity. The solution thus obtained was
allowed to react with diene (0.30 mmol) at the appropriate temperature
6 Organic cations: (a) Recent Developments in Carbocation and Onium
Ion Chemistry, ACS Symposium Ser., 965, ed. K. K. Laali,
American
Chemical
Society,
Washington
DC,
2007;
(see the ESIw) for 0.5 h. Then the reaction was quenched with Et3N
a solution containing diene
b
(1.0 mL). Initiation method B:
(b) Carbocation Chemistry, ed. G. A. Olah and G. K. S. Prakash,
Wiley, New Jersey, 2004; (c) G. A. Olah and K. K. Laali, Q. Wang
and G. K. S. Prakash, Onium Ions, Wiley, New York, 1998.
7 (a) K. Matsumoto, S. Fujie, K. Ueoka, S. Suga and J. Yoshida,
Angew. Chem., Int. Ed., 2008, 47, 2506. See also: (b) S. Suga,
K. Matsumoto, K. Ueoka and J. Yoshida, J. Am. Chem. Soc.,
2006, 128, 7710; (c) K. Matsumoto, K. Ueoka, S. Fujie, S. Suga
and J. Yoshida, Heterocycles, 2008, 76, 1103.
(0.30 mmol) and ArSSAr (Ar = p-MeOC6H4; 1.00 mmol) in 0.1 M
Bu4NB(C6F5)4–CH2Cl2 (8 mL) was electrolyzed (0.20 F molꢀ1 based
on diene) under constant-current conditions at the appropriate
c
temperature. Yield of isolated product unless otherwise stated.
d
Yield determined by 1H NMR using (Cl2CH)2 as an internal
e
standard. 0.3 F molꢀ1 based on the diene was used.
8 Addition of a cation to a carbon–carbon double bond: (a) S. Suga,
T. Nishida, D. Yamada, A. Nagaki and J. Yoshida, J. Am. Chem.
Soc., 2004, 126, 14338; (b) H. Mayr, Angew. Chem., Int. Ed. Engl.,
1990, 29, 1371.
9 For example: (a) W. A. Smit, R. Caple and L. P. Smoliakova,
Chem. Rev., 1994, 94, 2359; (b) D. J. Fox, D. House and S. Warren,
Angew. Chem., Int. Ed., 2002, 41, 2462; (c) S. E. Denmark,
W. R. Collins and M. D. Cullen, J. Am. Chem. Soc., 2009, 131,
3490, and references therein.
10 Reactivity of cations: (a) H. Mayr, B. Kempf and A. R. Ofial,
Acc. Chem. Res., 2003, 36, 66; (b) H. Mayr, T. Bug, M. F. Gotta,
N. Hering, B. Irrgang, B. Janker, B. Kempf, R. Loos, A. R. Ofial,
G. Remennikov and H. Schimmel, J. Am. Chem. Soc., 2001, 123, 9500.
11 N. S. Itter and E. Steckhan, Tetrahedron, 1987, 43, 2475.
12 E. Steckhan, Angew. Chem., Int. Ed. Engl., 1986, 25, 683.
the full range of reactivity of electrochemically generated
‘‘ArS+’’ and to gain deeper insight into the mechanistic details
of cation chain reactions initiated by this highly reactive
species.
This work was financially supported in part by a Grant-
in-Aid for Scientific Research from the Japan Society
for the Promotion of Science. We are also grateful to
Nippon Shokubai Co. and Nippoh Chemicals Co. for
providing NaB(C6F5)4 as a precursor of Bu4NB(C6F5)4. K.M
acknowledges JSPS for financial support.
ꢁc
This journal is The Royal Society of Chemistry 2009
5450 | Chem. Commun., 2009, 5448–5450