H. Sajiki et al.
less solid. 1H NMR (400 MHz, CDCl3): d=7.32 (d, J=8.6 Hz, 2H), 7.23
(d, J=8.6 Hz, 2H), 3.69 (s, 3H), 3.62 (s, 2H), 3.12 ppm (s, 3H); 13C NMR
(100 MHz, CDCl3): d=171.4, 148.3, 133.4, 131.0, 122.1, 52.2, 40.4,
37.3 ppm; MS (EI): m/z (%): 244 (85) [M+], 185 (75), 166 (42), 107
(100), 78 (34), 44 (30); HRMS (EI): m/z: calcd for C10H12O5S: 244.0405;
found: 244.0396; elemental analysis (%) calcd for C10H12O5S: C 49.17, H
4.95; found: C 49.08, H 4.99.
the filtrate was partitioned between diethyl ether (10 mL) and water
(10 mL). The aqueous layer was extracted with diethyl ether (310 mL),
and the combined organic layers were washed with brine (10 mL), dried
with anhydrous MgSO4, filtered, and concentrated under reduced pres-
sure.
4-Phenylphenyl methanesulfonate (6i): Following the general procedure
for the preparation of aryl mesylates, reaction of 4-hydroxybiphenyl
(1.70 g, 10.0 mmol), triethylamine (1.67 mL, 12.0 mmol), and methanesul-
fonyl chloride (0.929 mL, 12.0 mmol) for 19 h, followed by recrystalliza-
tion (ethyl acetate/n-hexane), gave 6i in 63% yield (1.57 g) as a colorless
solid. 1H NMR (400 MHz, CDCl3): d=7.62 (d, J=8.8 Hz, 2H), 7.55 (d,
J=7.3 Hz, 2H), 7.45 (d, J=7.3 Hz, 2H), 7.39–7.35 (m, 3H), 2.97 ppm (s,
3H); 13C NMR (100 MHz, CDCl3): d=148.5, 140.6, 139.7, 128.9, 128.7,
127.7, 127.1, 122.3, 37.3 ppm; MS (EI): m/z (%): 248 (43) [M+], 169
(100), 141 (45), 115 (28); HRMS (EI): m/z: calcd for C13H12O3S [M+]:
248.0507; found: 248.0500; elemental analysis (%) calcd for C13H12O3S: C
62.88, H 4.87; found: C 62.79, H 4.93.
[1] a) G. A. Perterson, F. Kung, J. S. McCallum, W. D. Wulff, Tetrahe-
dron Lett. 1987, 28, 1381–1384; b) D. A. Evans, M. R. Wood, B. W.
Trotter, T. I. Richardson, J. C. Barrow, J. L. Katz, Angew. Chem.
1998, 110, 2864–2868; Angew. Chem. Int. Ed. 1998, 37, 2700–2704.
[2] a) T. Severin, I. Ipach, Synthesis 1973, 796; b) M. Konieczny, R. G.
Harvey, J. Org. Chem. 1979, 44, 4813–4816; c) M. Node, K. Nishide,
K. Ohta, E. Fujita, Tetrahedron Lett. 1982, 23, 689–692.
[3] P. Sebçk, T. Tꢁmꢂr, T. Eszenyi, T. Patonay, J. Org. Chem. 1994, 59,
6318–6321, and references therein.
[4] a) H. Rottendorf, S. Sternhell, Aust. J. Chem. 1963, 16, 647–657;
b) K. Clauss, H. Jensen, Angew. Chem. 1973, 85, 981–982; Angew.
Chem. Int. Ed. Engl. 1973, 12, 918; c) W. Lonsky, H. Traitler, K.
Kratzl, J. Chem. Soc. Perkin Trans. 1 1975, 169–170; d) L. R. Subra-
manian, A. G. Martinez, A. H. Fernandez, R. M. Alvarez, Synthesis
1984, 481–485; e) S. Cacchi, P. G. Ciattini, E. Morera, G. Orter, Tet-
rahedron Lett. 1986, 27, 5541–5544; f) Q.-Y. Chen, Y.-B. He, Z.-Y.
Yang, J. Chem. Soc. Chem. Commun. 1986, 1452–1453; g) W. Cabri,
S. D. Bernardinis, F. Francalanci, S. Penco, J. Org. Chem. 1990, 55,
350–353; h) J. M. Saꢂ, M. Dopico, G. Martorell, A. Garcia-Raso, J.
Org. Chem. 1990, 55, 991–995; i) K. Sasaki, M. Sakai, Y. Sakakibara,
K. Takagi, Chem. Lett. 1991, 2017–2018; j) H. Kotsuki, P. K. Datta,
H. Hayakawa, H. Suenaga, Synthesis 1995, 1348–1350; k) K. Sasaki,
T. Kubo, M. Sakai, Y. Kuroda, Chem. Lett. 1997, 617–618; l) B. H.
Lipshutz, D. J. Buzard, R. W. Vivian, Tetrahedron Lett. 1999, 40,
6871–6874; m) B. H. Lipshutz, B. A. Frieman, T. Butler, V. Kogan,
Angew. Chem. 2006, 118, 814–817; Angew. Chem. Int. Ed. 2006, 45,
800–803.
[5] A polymer-supported aryl sulfonate as a leaving group; see: a) Y.
Pan, C. P. Holmes, Org. Lett. 2001, 3, 2769–2771; b) A. N. Cam-
midge, Z. Ngaini, Chem. Commun. 2004, 1914–1915; c) J. D. Revell,
A. Ganesan, Chem. Commun. 2004, 1916–1917.
[6] E. Vowinkel, C. Wolff, Chem. Ber. 1974, 107, 1213–1220.
[7] a) P. A. Sartretto, F. J. Sowa, J. Am. Chem. Soc. 1937, 59, 603–606;
b) Y. K. Sawa, N. Tsuji, S. Maeda, Tetrahedron 1961, 15, 144–153;
c) Y. K. Sawa, N. Tsuji, S. Maeda, Tetrahedron 1961, 15, 154–159;
d) W. H. Pirkle, J. L. Zabriskie, J. Org. Chem. 1964, 29, 3124–3126.
[8] a) W. J. Musliner, J. W. Gates Jr., J. Am. Chem. Soc. 1966, 88, 4271–
4273; b) B. J. Hussey, R. A. W. Johnstone, I. D. Entwistle, Tetrahe-
dron 1982, 38, 3775–3781.
[9] a) W. Pelletier, D. M. Locke, J. Org. Chem. 1958, 23, 131–133;
b) G. W. Kenner, N. R. Williams, J. Chem. Soc. 1955, 522–525;
c) A. H. Goldkamp, W. M. Hoehn, R. A. Mikulec, E. F. Nutting,
D. L. Cook, J. Med. Chem. 1965, 8, 409–414; d) R. A. Rossi, J. F.
Bunnett, J. Org. Chem. 1973, 38, 2314–2318; e) S. J. Shafer, W. D.
Closson, J. M. F. van Dijk, O. Piepers, H. M. Buck, J. Am. Chem.
Soc. 1977, 99, 5118–5123; f) S. J. Dominianni, C. W. Ryan, C. W.
DeArmitt, J. Org. Chem. 1977, 42, 344–346; g) S. C. Welch, M. E.
Walters, J. Org. Chem. 1978, 43, 4797–4799; h) T. Shono, Y. Matsu-
mura, K. Tsubata, Y. Sugihara, J. Org. Chem. 1979, 44, 4507–4511.
[10] H. Sajiki, A. Mori, T. Mizusaki, T. Ikawa, T. Maegawa, K. Hirota,
Org. Lett. 2006, 8, 987–990.
[11] H. Sajiki, T. Ikawa, K. Hirota, Org. Lett. 2004, 6, 4977–4980.
[12] a) H. Sajiki, A. Kume, K. Hattori, K. Hirota, Tetrahedron Lett. 2002,
43, 7247–7250; b) H. Sajiki, A. Kume, K. Hattori, H. Nagase, K.
Hirota, Tetrahedron Lett. 2002, 43, 7251–7254; c) Y. Monguchi, A.
Kume, K. Hattori, T. Maegawa, H. Sajiki, Tetrahedron 2006, 62,
7926–7933.
2-Benzylphenyl methanesulfonate (6 f): Following the general procedure
for the preparation of aryl mesylates, reaction of 2-benzylphenol (1.84 g,
10.0 mmol), triethylamine (1.67 mL, 12.0 mmol), and methanesulfonyl
chloride (0.929 mL, 12.0 mmol) for 2 h, followed by flash column chroma-
tography on silica gel (n-hexane/Et2O 10:1), gave 6 f in 96% yield
(2.51g) as a colorless solid. 1H NMR (400 MHz, CDCl3): d=7.39 (d, J=
7.8 Hz, 1H), 7.31–7.18 (m, 8H), 4.08 (s, 2H), 2.97 ppm (s, 3H); 13C NMR
(100 MHz, CDCl3): d=147.6, 139.5, 133.8, 131.6, 128.9, 128.5, 127.8,
127.2, 126.3, 121.7, 37.7, 36.2 ppm; MS (EI): m/z (%): 262 (52) [M+], 183
(100), 181 (85), 165 (50); HRMS (EI): m/z: calcd for C14H14O3S [M+]:
262.0664; found: 262.0670; elemental analysis (%) calcd for C14H14O3S: C
64.10, H 5.38; found: C 64.00, H 5.49.
Methyl 4-methylsulfonyloxybenzoate (6m): Following the general proce-
dure for the preparation of aryl mesylates, reaction of methyl 4-hydroxy-
benzoate (1.52 g, 10.0 mmol), triethylamine (1.67 mL, 12.0 mmol), and
methanesulfonyl chloride (0.929 mL, 12.0 mmol) for 20 h, followed by
flash column chromatography on silica gel (n-hexane), gave 6m in 94%
1
yield (2.17 g) as a colorless solid. The H NMR spectrum of 6m was iden-
tical with that given in the literature.[24]
Methyl 3-methylsulfonyloxybenzoate (6o): Following the general proce-
dure for the preparation of aryl mesylates, reaction of methyl 3-hydroxy-
benzoate (1.52 g, 10.0 mmol), triethylamine (1.67 mL, 12.0 mmol), and
methanesulfonyl chloride (0.929 mL, 12.0 mmol) for 20 h, followed by
flash column chromatography on silica gel (n-hexane), gave 6o in 94%
1
yield (2.17 g) as a colorless solid. The H NMR spectrum of 6o was iden-
tical with that given in the literature.[24]
4-Benzylphenyl methanesulfonate (6e): Following the general procedure
for the preparation of aryl mesylates, reaction of methyl 4-benzylphenol
(1.84 g, 10.0 mmol), triethylamine (1.67 mL, 12.0 mmol), and methanesul-
fonyl chloride (0.929 mL, 12.0 mmol) for 5 h, without subsequent purifi-
cation, gave 6e in 99% yield (2.59 g) as a colorless solid. 1H NMR
(400 MHz, CDCl3): d=7.32–7.16 (m, 9H), 3.98 (s, 2H), 3.11 ppm (s, 3H);
13C NMR (100 MHz, CDCl3): d=147.6, 140.6, 140.2, 130.3, 128.9, 128.6,
126.4, 121.9, 41.3, 37.3 ppm; MS (EI): m/z (%): 262 (100) [M+], 183 (80),
155 (67); HRMS (EI): m/z: calcd for C14H14O3S [M+]: 262.0664; found:
262.0660; elemental analysis (%) calcd for C14H14O3S: C 64.10, H 5.38;
found: C 64.10, H 5.40.
1-Naphthalenyl methanesulfonate (6j): Following the general procedure
for the preparation of aryl mesylates, reaction of methyl 1-naphthol
(1.44 g, 10.0 mmol), triethylamine (1.67 mL, 12.0 mmol), and methanesul-
fonyl chloride (0.929 mL, 12.0 mmol) for 2 h, without subsequent purifi-
cation, gave 6j in 97% yield (2.16 g) as a brown oil. The 1H NMR spec-
trum of 6j was identical with that given in the literature.[4g]
Generalprocedure for Tabel 7 : After two vacuum/Ar cycles to remove
air from the reaction tube, a mixture of aryl triflate (250 mmol), 10% Pd/
C
(10 wt% of the substrate), and Mg metal (7.3 mg, 300 mmol) in
[13] T. Junk, W. J. Catallo, Chem. Soc. Rev. 1997, 26, 401–406.
[14] D. E. Frantz, D. G. Weaver, J. P. Carrey, M. H. Kress, U. H. Dolling,
Org. Lett. 2002, 4, 4717–4718.
CH3OD (1.0 mL) was stirred at ordinary pressure (balloon) and tempera-
ture (ca. 208C) for the appropriate time. The reaction mixture was fil-
tered by using a membrane filter (Millipore, Millex-LH, 0.45 mm), and
[15] D. Macmillan, D. W. Anderson, Org. Lett. 2004, 6, 4659–4662.
1440
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 1432 – 1441