DEDICATED CLUSTER
UPDATES
Diarylmethanols by Catalyzed Asymmetric Aryl Transfer Reactions
2
D
0
1
6
7.28C; [a] : +16.3 (c 1.5, CHCl ). HNMR (400 MHz, ace-
Acknowledgements
3
tone-d ): d=2.27 (s, 3H, CH ), 4.76 (d, J=4.4 Hz, 1H, OH),
6
3
5
.81 (d, J=4.4 Hz, 1H, CH), 6.98 (dd, J=5.0/0.8 Hz, 1H,
This work was supported by the Fonds der Chemischen In-
dustrie and the Deutsche Forschungsgemeinschaft (DFG)
within the Collaborative Research Center (SFB) 380 ꢀAsym-
metric Synthesis by Chemical and Biological Methodsꢁ and
the Graduate School GRK 440. J. R. thanks DaimlerChrysler
fora schola rs hip.
CH ), 7.11 (d, J=8.0 Hz, 2H, CH ), 7.22–7.25 (m, 1H,
CH ), 7.28 (d, J=8.0 Hz, 2H, CH ), 7.30–7.33 (m, 1H,
CH ); C NMR (100 MHz, acetone-d ): d=20.3 (CH ), 71.9
ar
ar
ar
ar
13
ar
6
3
(
CH), 120.4 (CH), 125.4 (CH), 126.3 (2CH), 126.6 (CH),
1
3
28.6 (2CH), 136.3 (C), 142.1 (C), 147.3 (C); IR (KBr): n=
À1
238, 1614, 1416, 1279, 1028, 820, 795, 766, 738, 689 cm ;
+
MS (EI, 70 eV): m/z (%)=204 (100, M ), 119 (86), 189 (18),
1
7
11 (40), 91 (24); anal. calcd. for C H OS (204.29): C
0.55, H5.92; found: C 70.42, H5.75. HPLC separation con-
12 12
References
ditions: Chiralcel AS, 210 nm, 98:2 heptane/i-PrOH,
À1
0.5 mLmin , t =33.5 min (S), 39.6 min (R).
R
[
1] A. F. Harms, W. Hespe, W. T. Nauta, R. F. Rekker,
Drug Design 1976, 6, 1.
[15]
(
R)-(2-Methylphenyl)-(2’-thienyl)methanol (3h)
[
2] R. F. Rekker, H. Timmerman, A. F. Harms, W. T.
The title compound was obtained from 2-methylphenyl-
boronic acid (1a) (81.5 mg, 0.6 mmol) and 2-thiophencarbal-
dehyde (2e) (28 mg, 23.4 mL, 0.25 mmol) according to the
general procedure after column chromatography (silica gel,
eluents: pentane/diethyl ether=8:2) as a white solid; yield:
Nauta, Arzneim. Forsch. 1971, 21, 688.
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Chilenski, C. J. McWilliams, Org. Lett. 2003, 5, 5039;
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J. Foricher, M. Lalonde, R. K. Muller, M. Scalone, G.
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2
0
0
.22 mmol (89%, 94% ee); mp 75.3–76.08C; [a] : À3 (c 1,
D
1
CHCl ). HNMR (400 MHz, acetone- d ): d=2.25 (s, 3H,
3
6
CH ), 5.05 (d, J=4.4 Hz, 1H, OH), 6.18 (d, J=4.4 Hz, 1H,
3
CH), 6.78–6.82 (m, 1H, CH ), 6.89 (dd, J=4.3 Hz/5.0 Hz
ar
1
5
H, CH ), 7.09–7.24 (m, 3H, CH ), 7.23 (dd, J=1.1 Hz/
a
r
a
r
.0 Hz, 1H, CH ) 7.61 (dd, J=1.1 Hz/7.4 Hz, 1H, CH );
ar
ar
1
3
C NMR (100 MHz, acetone-d ): d=18.5 (CH ), 68.5 (CH),
6
3
124.4 (CH), 124.8 (CH), 125.8 (CH), 126.0 (CH), 126.2
(
CH), 127.2 (CH), 130.1 (CH), 134.8 (C), 142.6 (C), 149.0
(
7
C); IR (KBr): n=3454, 3365, 1635, 1459, 1289, 1222, 1021,
85, 757, 700 cm ; MS (EI, 70 eV): m/z (%)=204 (31, M ),
À1
+
1
71 (10), 119 (100), 91 8 (19); anal. calcd. for C H OS
1
2
12
(
204.29): C 70.55, H5.92; found: C 70.64, H6.26. HP LC
separation conditions: Chiralcel AD, 210 nm, 99:1 heptane/
[5] a) W.-S. Huang, L. Pu, J. Org. Chem. 1999, 64, 4222;
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Angew. Chem. 2000, 112, 3607; Angew. Chem. Int. Ed.
À1
i-PrOH, 0.7 mLmin , t =31.5 min (S), 40.0 min (R).
R
[9b]
(
R)-(2-Furanyl)-(2’-methylphenyl)methanol (3i)
The title compound was obtained from 2-methylphenyl-
boronic acid (1a) (81.5 mg, 0.6 mmol) and furan-2-carbalde-
hyde (2f) (24 mg, 0.25 mmol) according to the general pro-
cedure after column chromatography (silica gel, eluents:
pentane/ethylacetate=9:1) as a pale yellow solid; yield:
2
000, 39, 3465; e) G. Zhao, X.-G. Li, X.-R. Wang, Tetra-
hedron: Asymmetry 2001, 12, 399; f) I. Schiffers, T.
Rantanen, F. Schmidt, W. Bergmans, L. Zani, C. Bolm,
J. Org. Chem. 2006, 71, 2320; g) D.-H. Ko, K. H. Kim,
D.-C. Ha, Org. Lett. 2002, 4, 3759; h) M. G. Pizzuti, S.
Superchi, Tetrahedron: Asymmetry 2005, 16, 2263; i) M.
Fontes, X. Verdaguer, L. Solà, M. A. Pericàs, A. Riera,
J. Org. Chem. 2004, 69, 2532; j) M. Hatano, T. Miyamo-
to, K. Ishihara, Adv. Synth. Catal. 2005, 347, 1561; k) 25
Y.-C. Qin, L. Pu, Angew. Chem. 2005, 118, 279; Angew.
Chem. Int. Ed. 2006, 45, 273; l) K. Ito, Y. Tomita, T.
Katsuki, Tetrahedron Lett. 2005, 46, 6083; m) J. Ru-
dolph, C. Bolm, P.-O. Norrby, J. Am. Chem. Soc. 2005,
2
D
0
0
0
.18 mmol (70%, 92% ee); mp 44.6–45.28C; [a] : À8.4 (c
1
.82, CH Cl ). HNMR (300 MHz, CDCl ): d=2.25 (s, 1H,
2
2
3
CH ), 2.42 (sbr, 1H, OH), 6.27–6.32 (m, 1H, CH), 7.11–7.29
3
(
m, 3H, CH ), 7.36–7.40 (m, 1H, CH ), 7.20–7.35 (m, 2H,
ar ar
13
CH ), 7.52–7.59 (m, 1H, H ); C NMR (75 MHz, CDCl ):
ar
ar
3
d=19.0 (CH ), 67.1 (CH), 107.6 (CH), 110.3 (CH), 126.1
3
(
(
1
CH), 126.2 (CH), 127.9 (CH), 130.4 (CH), 135.3 (C), 138.9
C), 142.5 (CH), 155.6 (C); IR (KBr): n=3178, 1600, 1463,
À1
145, 1045, 1006, 729 cm ; MS (EI, 70 eV): m/z (%)=188
1
27, 1548; n) A. L. Braga, D. S. Lüdtke, F. Vargas,
+
(
100, M ), 171 (18), 119 (39), 97 (24), 91 (33); anal. calcd.
M. W. Paix¼o, Chem. Commun. 2005, 2512; o) A. L.
Braga, S. S. Lüdtke, P. H. Schneider, F. Vargas, A.
Schneider, L. A. Wessjohann, M. W. Paix¼o, Tetrahe-
dron Lett. 2005, 46, 7827; p) J.-X. Ji, J. Wu, T. T.-L. Au-
Yeung, C.-W. Yip, R. K. Haynes, A. S. C. Chan, J. Org.
Chem. 2005, 70, 1093; q) S. ÖzÅubukÅu, F. Schmidt, C.
Bolm, Org. Lett. 2005, 7, 1407; r) P.-Y. Wu, H.-L. Wu,
B.-J. Uang, J. Org. Chem. 2006, 71, 833; s) W.-S. Huang,
Q.-S. Hu, L. Pu, J. Org. Chem. 1999, 64, 7940.
for C H O (188.22): C 76.57, H6.43; found C 76.68, H
12
12
2
6
9
3
.74. HPLC separation conditions: Chiralcel AD, 210 nm,
7:3 heptane/i-PrOH, 0.6 mLmin , tR =31.0 min (S),
3.2 min (R).
À1
Adv. Synth. Catal. 2007, 349, 703 – 708
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707