LETTER
Scope of Tyrosine O-Arylations with Boronic Acids
723
Experimental Procedure for the Preparation of Isodityrosine 13
Copper(II) acetate (11.7 mg, 0.064 mmol, 20 mol%) was suspended
in DCE (2 mL). Pyridine (130 mL, 1.6 mmol, 5 equiv) was added
and the suspension was stirred for 10 min under O2 (1 atm). Phenol
1b (152 mg, 0.32 mmol) and powdered 4 Å MS (800 mg) were add-
ed. Boronic acid 17 (200 mg, 0.45 mmol, 1.4 equiv) was dissolved
in DCE (5 mL) and slowly added to the mixture (300 mL/h). The
slurry was stirred under O2 (1 atm) for 48 h, diluted with EtOAc,
and filtered over a pad of SiO2. Flash column chromatography (cy-
clohexane–EtOAc, 70:30) gave isodityrosine 13 (256 mg, 92%) as
(6) Nishiyama, S.; Nakamura, K.; Suzuki, Y.; Yamamura, S.
Tetrahedron Lett. 1986, 27, 4481.
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(8) (a) Olivera, R.; SanMartin, R.; Churruca, F.; Domínguez, E.
J. Org. Chem. 2002, 67, 7215. (b) Cai, Q.; Zou, B.; Ma, D.
Angew. Chem. Int. Ed. 2006, 45, 1276. (c) Cai, Q.; He, G.;
Ma, D. J. Org. Chem. 2006, 71, 5268.
(9) Chapman, C. J.; Matsuno, A.; Frost, C. G.; Willis, M. C.
Chem. Commun. 2007, 3903.
(10) (a) Chan, D. M. T.; Monaco, K. L.; Wang, R.-P.; Winters,
M. P. Tetrahedron Lett. 1998, 39, 2933. (b) Evans, D. A.;
Katz, J. L.; West, T. R. Tetrahedron Lett. 1998, 39, 2937.
(c) Lam, P. Y. S.; Clark, G. C.; Saubern, S.; Adams, J.;
Winters, M. P.; Chan, D. M. T.; Combs, A. Tetrahedron
Lett. 1998, 39, 2941. Reviews: (d) Ley, S. V.; Thomas, A.
W. Angew. Chem. Int. Ed. 2003, 42, 5400. (e) Chan, D. M.
T.; Lam, P. Y. S. In Boronic Acids; Hall, D., Ed.; Wiley-
VCH: Weinheim, 2005, 205.
(11) (a) Evans, D. A.; Katz, J. L.; Peterson, G. S.; Hintermann, T.
J. Am. Chem. Soc. 2001, 123, 12411. (b) Deng, H.; Jung,
J. K.; Liu, T.; Kuntz, K. W.; Snapper, M. L.; Hoveyda,
A. H. J. Am. Chem. Soc. 2003, 125, 9032. (c) Shinohara, T.;
Deng, H.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc.
2005, 127, 7334.
1
a colorless solid: mp 56–58 °C, [a]D –52.7 (c 0.98, MeOH). H
NMR (500 MHz, DMSO-d6): d = 1.21 (s, 4.42 H)*, 1.26 (s, 4.37
H)*, 1.34 (s, 3.98 H)*, 1.38 (s, 4.6 H)*, 2.57 (m, 3 H), 2.62 (s, 1.37
H)*, 2.68 (s, 1.52 H)*, 2.92 (m, 2 H), 3.09 (m, 2 H), 3.68 (m, 3 H),
4.26 (m, 2 H), 4.44 (m, 1 H), 4.65 (m, 1 H), 4.74 (m, 1 H), 5.12 (d,
2 H, J = 15.4 Hz), 6.67 (dd, 2 H, J = 8.2, 23.6 Hz), 6.81 (m, 2 H),
7.03 (dd, J = 9.8 Hz, 3 H), 7.36 (m, 9 H), 7.51 (d, J = 7.1 Hz, 0.35
H)*, 7.56 (d, J = 7.5 Hz, 1.65 H)*, 7.87 (d, J = 7.5 Hz, 2 H). 13C
NMR (126 MHz, DMSO-d6): d = 27.4, 31.6, 33.1, 35.7, 46.3, 55.5,
59.6, 65.9, 69.5, 79.1, 80.8, 113.2, 115.9, 120.0, 122.0, 125.7,
127.3, 127.3, 127.9, 128.5, 130.0, 131.1, 136.0, 143.7, 143.6, 149.8,
154.5, 156.6, 155.6, 156.4, 170.3; *carbamate rotamers induce sig-
nal splitting. ESI-HRMS: m/z calcd: 871.4164 [M + H+], found:
871.4172.
(12) Hitotsuyanagi, Y.; Ishikawa, H.; Naito, S.; Takeya, K.
Tetrahedron Lett. 2003, 44, 5901.
(13) Lam, P. Y. S.; Vincent, G.; Clark, C. G.; Deudon, S.; Jadhav,
P. K. Tetrahedron Lett. 2001, 42, 3415.
Acknowledgment
B.K. was recipient of an IMPRS Chemical Biology predoctoral fel-
lowship. H.-D.A. acknowledges support from the DFG (Emmy-
Noether program).
(14) All peptides were accessed by standard solid-phase peptide
synthesis protocols on 2-Cl-trityl or Rink-amide resins,
when appropriate, using Fmoc-protected amino acids and
HOBt, HBTU, and EtN(i-Pr)2 as coupling reagents.
(15) Chiarello, J.; Joullie, M. M. Synth. Commun. 1988, 18, 2211.
(16) Review: Aurelio, L.; Brownlee, R. T. C.; Hughes, A. B.
Chem. Rev. 2004, 104, 5823.
(17) Olsen, R. K. J. Org. Chem. 1970, 35, 1912.
(18) Ishiyama, T.; Murata, M.; Miyaura, N. J. Org. Chem. 1995,
60, 7508.
References and Notes
(1) Overview: Feliu, L.; Planas, M. Int. J. Pept. Res. Ther. 2005,
11, 53.
(2) Kahne, D.; Leimkuhler, C.; Wei, L.; Walsh, C. Chem. Rev.
2005, 105, 425.
(3) Waldmann, H.; He, Y.-P.; Tan, H.; Arve, L.; Arndt, H.-D.
(19) Falck, J. R.; Bondlela, M.; Ventkatamaran, S. K.; Srinivas,
D. J. Org. Chem. 2001, 66, 7148.
Chem. Commun. 2008, 5562.
(4) Itokawa, H.; Takeya, K. Heterocycles 1993, 35, 1467.
(5) Frlan, R.; Kikelj, D. Synthesis 2006, 2271.
Synlett 2009, No. 5, 720–723 © Thieme Stuttgart · New York