M. Arisawa et al. / Tetrahedron Letters 46 (2005) 5669–5671
5671
O
O
O
O
RhH(PPh3)4 (5 mol%)
dppe (10 mol%)
CO2Me
X
P
X
P
CO2Me
HN
R
R
R
R
H
HN
H
NHCO2t-Bu
CO2Me
+
N
X
P
NHCO2t-Bu
CO2Me
N
R
R
acetone, refl., 0.5 h
S
S
2
X = S, R = Me 70%
X = O, R = Ph 71%
Scheme 4.
RhH(PPh3)4 (2 mol%)
dppe (4 mol%)
S
P
S
Me
Me
Me
+
RSSR
SPh
P
SR
Me
acetone, refl., 0.5 h
R = p-ClC6H4 68%
R = p-MeC6H4 69%
R = n-C8H17 71%
R = t-BuOCONH(CH2)2 81%
R = MeO2C(CH2)3 70%
R = MeO(CH2)4 74%
Scheme 5.
Manthey, M. K.; Huang, D. T. C.; Bubb, W. A.;
Christopherson, R. I. J. Med. Chem. 1998, 41, 4550; Au-
Yeung, T.-L.; Chan, K.-L.; Chan, W.-K.; Haynes, R. K.;
Williams, I. D.; Yeung, L. L. Tetrahedron Lett. 2001, 42,
453.
to synthesize dithiophosphinates from disulfides. The
treatment of phenyl dimethyldithiophosphinate and
di(p-chlorophenyl) disulfide (1 equiv) in the presence of
RhH(PPh3)4 (2 mol%) and dppe (4 mol%) in refluxing
acetone for 0.5 h gave p-chlorophenyl dimethyl-
dithiophosphinate in 68% yield (Scheme 5). Several
dialkyl disulfides also underwent the exchange reaction.
2. Tsvetkov, E. N.; Chepaikina, T. A.; Kabachnik, M. I. Izv.
Akad., Nauk SSSR Ser. Khim. 1979, 394; Also see Kuchen,
W.; Knop, B. Angew. Chem. 1964, 76, 496.
3. Ando, F.; Higuchi, T.; Fujimura, Y.; Koketsu, J.
Memoirs Coll. Eng., Chubu Univ. 1991, 27, 193 (CAN
117:90379).
4. Szafraniec, L. J.; Reiff, L. P.; Aaron, H. S. J. Am. Chem.
Soc. 1970, 92, 6391; Lopusinski, A.; Luczak, L.; Michalski,
J. Tetrahedron 1982, 38, 679; Skrzypczynski, Z.; Michalski,
J. J. Org. Chem. 1988, 53, 4549; Lopusinski, A. Phosphorus,
Sulfur, Silicon 1989, 45, 137.
To summarize, a rhodium complex catalyzes thio-
phosphinylation and phosphinylation of disulfides or
diselenides by S–S/P–P, Se–Se/P–P, or S–S/P–S bond
metathesis. Use of disulfides in the synthesis of organo-
sulfur compounds in place of thiols would have syn-
thetic potential, when a suitable catalyst is developed.
5. Arisawa, M.; Yamaguchi, M. J. Am. Chem. Soc. 2003, 125,
6624; Arisawa, M.; Tanaka, K.; Yamaguchi, M. Tetrahe-
dron Lett. 2005, 46, 4797.
Acknowledgments
6. Arisawa, M.; Fujimoto, K.; Morinaka, S.; Yamaguchi, M.
J. Am. Chem. Soc., submitted for publication.
This work was supported by JSPS (Nos. 16109001 and
17689001). M.A. expresses her thanks for financial sup-
port from the New Energy and Industrial Technology
Development Organization (NEDO) of Japan (No.
02A44003d) and the Takeda Science Foundation.
7. In a two-necked flask equipped with a reflux condenser
were placed RhH(PPh3)4 (1.5 mol%, 13.8 mg), 1,2-bis(di-
phenylphosphino)ethane (dppe, 3.0 mol%, 9.6 mg), tetra-
methylbiphosphine disulfide (0.8 mmol, 149.0 mg), and
diphenyl disulfide (0.8 mmol, 174.4 mg) in acetone
(3.0 mL) under an argon atmosphere, and the solution
was heated at reflux for 0.5 h. Then, the solvent was
removed under reduced pressure, and the residue was
purified by flash column chromatography on silica gel
giving phenyl dimethyldithiophosphinate (295.2 mg, 91%).
8. Segi, M.; Kato, M.; Nakajima, T.; Suga, S.; Sonoda, N.
Chem. Lett. 1989, 1009; Murai, T.; Kimura, T.; Miwa, A.;
Kurachi, D.; Kato, S. Chem. Lett. 2002, 914; Kimura, T.;
Murai, T. J. Org. Chem. 2005, 70, 952.
References and notes
1. Examples Yoshifuji, M.; Hanafusa, F.; Inamoto, N.
Chem. Lett. 1979, 723; Ueki, M.; Shinozaki, K. Bull.
Chem. Soc. Jpn. 1983, 56, 1187; Horner, L.; Lindel,
H. Chem. Ber. 1985, 118, 676; Omelanczuk, J.; Miko-
lajczyk, M. J. Chem. Soc., Chem. Commun. 1994, 2223;