6948
Q. Dai et al. / Tetrahedron 64 (2008) 6943–6948
2
.92 (m, 1H), 2.51–2.54 (m, 3H), 2.24–2.31 (m, 2H), 1.24 (d,
J¼14.2 Hz, 9H), 0.46 (s, 9H); 13C NMR (CD
2 2
Cl , 75 MHz) d 135.9,
135.8, 134.4 (d, J¼2.0 Hz), 134.3, 134.2, 133.3, 131.4, 130.6, 130.5,
13
J¼15.0 Hz, 9H); C NMR (CD
34.2 (d, J¼7.4 Hz), 133.3 (d, J¼12.8 Hz), 132.6, 132.5, 132.4, 132.3,
31.7, 131.6, 131.2, 131.1, 130.3, 129.7, 129.6, 129.3, 128.8, 128.7, 128.6,
28.3, 128.1, 128.0, 127.7, 127.4, 127.3, 127.0, 126.8, 126.5, 125.3, 102.8
2
Cl
2
, 100 MHz)
d
134.9 (d, J¼7.4 Hz),
1
1
1
130.4, 130.3, 128.9, 128.5, 128.4, 128.2 (d, J¼3.6 Hz), 127.9, 127.3,
127.0, 126.6, 126.5, 104.0 (t, J¼7.0 Hz), 98.9 (dd, J¼6.5, 10.1 Hz), 96.5
(t, J¼7.4 Hz), 91.7 (dd, J¼6.8, 11.0 Hz), 56.8 (d, J¼13.9 Hz), 41.7 (d,
(
2
(
d, J¼6.7 Hz), 99.0, 96.4, 68.1 (d, J¼23.9 Hz), 59.3, 50.5, 29.9, 29.4,
J¼4.1 Hz), 39.3, 37.9, 32.6, 32.1, 31.9 (d, J¼4.3 Hz), 30.9, 28.7 (d,
31
31
8.6, 27.4, 26.9 (dd, J¼2.3, 4.5 Hz), 25.7 (d, J¼14.8 Hz); P NMR
J¼3.9 Hz), 28.4, 28.0; P NMR (CD
2
Cl
2
, 145 MHz)
d
36.26 (dd,
þ
CD
2
Cl
2
, 145 MHz)
d
22.92 (dd, J¼72.1, 127.1 Hz), ꢀ23.11 (dd, J¼72.1,
J¼36.5, 127.3 Hz), 26.32 (dd, J¼36.3, 133.4 Hz); HRMS (ESI ) calcd
þ
ꢀ
134.2 Hz); HRMS (ESI ) calcd for C46
H
46
P
2
Rh (cation) 763.2130,
for C42
54
H P
2
Rh (cation) 723.2697, found 723.2756; HRMS (ESI )
(anion) 87.0029, found 87.0019.
ꢀ
found 763.2094; HRMS (ESI ) calcd for BF
4
(anion) 87.0029, found
calcd for BF
4
8
7.0023.
Acknowledgements
4
.4.2. [Rh(cod)1b]BF
4
(9b)
1
H NMR (CD
2
Cl
2
, 360 MHz) d 8.18–8.23 (m, 1H), 8.07 (d,
This work was supported by the National Institutes of Health
J¼8.4 Hz, 1H), 7.96 (d, J¼8.5 Hz, 1H), 7.86 (d, J¼8.1 Hz, 1H), 7.80 (d,
J¼8.4 Hz, 1H), 7.76 (d, J¼8.1 Hz, 1H), 7.70 (d, J¼8.4 Hz, 1H), 7.62 (t,
J¼7.6 Hz, 1H), 7.37–7.42 (m, 2H), 7.24 (t, J¼7.7 Hz, 1H), 6.99–7.11 (m,
(GM58832).
3
1
H), 6.66–6.69 (m, 2H), 6.50 (t, J¼7.5 Hz, 1H), 6.35 (dd, J¼3.3, 7.3 Hz,
H), 6.09–6.20 (m, 3H), 6.02 (d, J¼8.6 Hz, 1H), 5.53 (s, 2H), 5.40 (br
References and notes
1. (a) Izumi, Y.; Tai, A. Stereo-differentiating Reactions: The Nature of Asymmetric
s, 1H), 5.10 (br s, 1H), 3.22–3.29 (m, 2H), 2.85 (d, J¼3.8 Hz, 2H), 2.27
3
1
Reactions; Academic: New York, NY, 1977; (b) Asymmetric Catalysis; Bosnich, B.,
Ed.; Martinus Nijhoff: New York, NY, 1986; (c) Catalytic Asymmetric Synthesis;
Ojima, I., Ed.; VCH: New York, NY, 1993; (d) Brunner, H.; Zettlmeier, W. Handbook
of Enantioselective Catalysis; VCH: Weinheim, 1993; (e) Noyori, R. Asymmetric
Catalysis in Organic Synthesis; Wiley: New York, NY, 1994; (f) Chiral Reactions in
Heterogeneous Catalysis; Jannes, G., Dubois, V., Eds.; Plenum: New York, NY, 1995;
(g) Applied Homogeneous Catalysis with Organometallic Compounds; Cornils, B.,
Herrmann, W. A., Eds.; VCH: Weinheim, 1996; Vols. 1 and 2; (h) Transition Metals
for Organic Synthesis: Building Blocks and Fine Chemicals; Beller, M., Bolm, C., Eds.;
Wiley-VCH: Weinheim, 1998; Vols. 1 and 2; (i) Comprehensive Asymmetric Ca-
talysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Vols.
1–3; (j) Catalytic Asymmetric Synthesis; Ojima, I., Ed.; Wiley-VCH: New York, NY,
(
s, 3H), 2.14–2.25 (m, 5H), 1.30 (d, J¼14.8 Hz, 9H), 1.10 (s, 3H);
P
NMR (CD
2
Cl
2
, 145 MHz)
d
26.52 (dd, J¼62.3, 131.3 Hz), ꢀ17.52 (dd,
þ
J¼63.5, 131.2 Hz); HRMS (ESI ) calcd for C48
50 2
H P Rh (cation)
ꢀ
7
8
91.2413, found 791.2443; HRMS (ESI ) calcd for BF
7.0029, found 87.0021.
4
(anion)
4
.4.3. [Rh(cod)1c]BF
4
(9c)
1
H NMR (CD
2
Cl
2
, 360 MHz)
d
8.18 (d, J¼8.3 Hz, 1H), 7.95–8.05
(
2
1
m, 4H), 7.52 (t, J¼7.2 Hz, 2H), 7.41 (d, J¼8.4 Hz, 1H), 7.21–7.29 (m,
2000.
H), 7.14 (d, J¼8.5 Hz,1H), 7.00 (d, J¼8.5 Hz,1H), 5.71 (s, 1H), 5.39 (s,
2
. (a) Noyori, R.; Kitamura, M. Modern Synthetic Methods; Scheffold, R., Ed.;
Springer: Berlin, 1989; Vol. 5, p 115; (b) Takaya, H.; Ohta, T.; Noyori, R. Catalytic
Asymmetric Synthesis; Ojima, I., Ed.; VCH: New York, NY, 1993; p 1; (c) Ohkuma,
T.; Noyori, R. Transition Metals for Organic Synthesis: Building Blocks and Fine
Chemicals; Beller, M., Bolm, C., Eds.; Wiley-VCH: Weinheim, 1998; Vol. 2, p 25.
. (a) Knowles, W. S.; Sabacky, M. J. J. Chem. Soc., Chem. Commun. 1968, 1445; (b)
Horner, L.; Siegel, H.; B u¨ the, H. Angew. Chem., Int. Ed. Engl. 1968, 7, 941.
. (a) Imamoto, T.; Watanabe, J.; Wada, Y.; Masuda, H.; Yamada, H.; Tsuruta, H.;
Matsukawa, S.; Yamaguchi, K. J. Am. Chem. Soc. 1998, 120, 1635; (b) Gridnev, I. D.;
Yamanoi, Y.; Higashi, N.; Tsuruta, H.; Yasutake, M.; Imamoto, T. Adv. Synth. Catal.
2001, 343, 118.
H), 5.32 (s, 1H), 5.08–5.15 (m, 2H), 3.66–3.69 (m, 3H), 3.40–3.43
(
2
m, 1H), 3.22–3.30 (m, 1H), 2.61 (q, J¼7.1 Hz, 2H), 2.31–2.34 (m, 5H),
.14–2.20 (m, 4H), 1.74–2.03 (m, 9H), 1.32–1.51 (m, 4H), 1.14 (d,
13
J¼14.7 Hz, 9H), 1.02–1.06 (m, 3H); C NMR (CD
134.9, 134.1, 133.7, 133.6, 133.4, 131.9, 131.8, 130.6, 130.1, 129.4,
29.3, 129.0, 128.6, 128.5, 128.1, 127.9, 127.8, 127.1, 127.0, 126.5, 103.7
2 2
Cl , 100 MHz)
3
4
d
1
(
t, J¼8.0 Hz), 97.4 (t, J¼8.0 Hz), 96.3 (t, J¼7.7 Hz), 91.2, 68.1, 52.2 (t,
J¼17.0 Hz), 38.8 (d, J¼9.6 Hz), 36.5, 35.5, 33.2, 32.8, 31.6, 31.4, 29.7,
5
6
. (a) Tang, W.; Zhang, X. Angew. Chem., Int. Ed. 2002, 41, 1612; (b) Tang, W.; Zhang,
X. Org. Lett. 2002, 4, 4159; (c) Tang, W.; Liu, D.; Zhang, X. Org. Lett. 2003, 5, 205.
. Tang, W.; Wang, W.; Chi, Y.; Zhang, X. Angew. Chem., Int. Ed. 2003, 42, 3509.
2
8.8, 28.5 (d, J¼9.0 Hz), 28.3 (d, J¼4.6 Hz), 28.2 (d, J¼6.0 Hz), 28.0
(
(
d, J¼8.5 Hz), 27.5 (d, J¼8.7 Hz), 27.2 (d, J¼3.9 Hz), 26.3, 26.0, 25.9
31
d, J¼15.1 Hz), 25.2, 25.1; P NMR (CD
2
Cl
2
, 145 MHz)
d
21.72 (dd,
7. Hoge, G.; Wu, H.-P.; Kissel, W. S.; Pflum, D. A.; Greene, D. J.; Bao, J. J. Am. Chem.
Soc. 2004, 126, 5966.
8. (a) Imamoto, T.; Oshiki, T.; Onozawa, T.; Kusumoto, T.; Kazuhiko, S. J. Am. Chem.
Soc. 1990, 112, 5244; (b) Juge, S.; Stephan, M.; Laffitte, J. A.; Genet, J. P. Tetrahe-
dron Lett. 1990, 31, 6357; (c) Corey, E. J.; Chen, Z.; Tanoury, G. J. J. Am. Chem. Soc.
þ
J¼59.8, 129.5 Hz), ꢀ6.09 (dd, J¼59.9, 125.4 Hz); HRMS (ESI ) calcd
ꢀ
for C46
H
58
P
2
Rh (cation) 775.3069, found 775.3003; HRMS (ESI )
(anion) 87.0029, found 87.0023.
calcd for BF
4
1993, 115, 11000; (d) Pietrusiewicz, K. M.; Zablocka, M. Chem. Rev. 1994, 94, 1375;
(
e) Muci, A. R.; Campos, K. R.; Evans, D. A. J. Am. Chem. Soc. 1995, 117, 9075; (f)
4
.4.4. [Rh(cod)1d]BF
4
(9d)
, 360 MHz)
H), 7.70 (d, J¼8.4 Hz, 1H), 7.43–7.50 (m, 3H), 7.14 (p, J¼7.5 Hz, 2H),
Ohff, M.; Holz, J.; Quirmbach, M.; Borner, A. Synthesis 1998, 1391; (g) Wolfe, B.;
Livinghouse, T. J. Am. Chem. Soc. 1998, 120, 5116; (h) Al-Masum, M.; Kumar-
aswamy, G.; Livinghouse, T. J. Org. Chem. 2000, 65, 4776; (i) Moncarz, J. R.; Lar-
itcheva, N. F.; Glueck, D. S. J. Am. Chem. Soc. 2002, 124, 13356; (j) Leung, P.-H. Acc.
Chem. Res. 2004, 37, 169.
1
H NMR (CD
2
Cl
2
d
8.10 (d, J¼8.4 Hz,1H), 7.91–7.99 (m,
3
7
5
.02 (d, J¼8.7 Hz, 1H), 6.71 (d, J¼8.7 Hz, 1H), 5.92 (t, J¼8.1 Hz, 2H),
.47 (t, J¼14.7 Hz, 1H), 5.43 (s, 1H), 5.04 (s, 1H), 3.29–3.40 (m, 2H),
.43–2.52 (m, 4H), 2.11–2.27 (m, 4H), 1.56 (d, J¼13.3 Hz, 9H), 1.19 (d,
9
. Drexler, H.-J.; You, J.; Zhang, S.; Fischer, C.; Baumann, W.; Spannenberg, A.;
Heller, D. Org. Process Res. Dev. 2003, 7, 355 and references cited therein.
2