Molybdenum(VI)-Catalyzed Direct Substitution of Allylic Alcohols
3430, 3058, 3025, 2360, 2339, 1597, 1492, 1449, 1090, 1027, 965,
746, 697, 538 cm–1.
84.9, 114.4, 127.0, 127.3, 127.5, 128.1, 128.2, 128.4, 128.6, 128.7,
128.9, 129.8, 130.8, 131.6, 133.6, 137.1, 141.7, 159.7, 159.8 ppm.
3gn and 3hn:[31] White solid (3gn/3hn, 33:67). Data for 3gn: 1H
NMR (300 MHz, CDCl3): δ = 1.96 (s, 3 H), 2.28 (s, 3 H), 3.81 (s,
3 H), 4.33–4.36 (m, 2 H), 6.08 (ddd, J = 1.2, 6.6, 15.9 Hz, 1 H),
6.40 (d, J = 15.9 Hz, 1 H), 6.84 (d, J = 9.0 Hz, 2 H), 7.19–7.32 (m,
7 H) ppm. Data for 3hn: 1H NMR (300 MHz, CDCl3): δ = 1.97 (s,
3 H), 2.28 (s, 3 H), 3.81 (s, 3 H), 4.33–4.36 (m, 2 H), 6.21 (ddd, J
= 3.9, 3.9, 15.6 Hz, 1 H), 6.43 (d, J = 15.6 Hz, 1 H), 6.89 (d, J =
9.0 Hz, 2 H), 7.19–7.32 (m, 7 H) ppm. Data for the mixture: 13C
NMR (75 MHz, CDCl3): δ = 29.8, 30.0, 48.4, 49.3, 55.3, 74.7,
114.0, 114.4, 126.4, 127.1, 127.2, 127.6, 127.7, 127.9, 128.5, 129.0,
129.4, 129.6, 131.1, 131.3, 132.0, 136.6, 140.4, 158.7, 159.3, 202.8,
203.0 ppm.
3al:[11a] Colorless oil. Yield: 128 mg, 83%. 1H NMR (300 MHz,
CDCl3): δ = 5.07 (d, J = 7.2 Hz, 1 H), 6.39 (d, J = 15.9 Hz, 1 H),
6.66 (dd, J = 7.2, 15.9 Hz, 1 H), 6.79 (s, 1 H), 7.03 (t, J = 7.2 Hz,
1 H), 7.15–7.43 (m, 13 H), 7.77 (br. s, 1 H) ppm.
3dl:[28] Yellow oil. Yield: 47 mg, 51%. 1H NMR (300 MHz,
CDCl3): δ = 1.78 (s, 3 H), 1.79 (s, 3 H), 3.48 (d, J = 7.2 Hz, 2 H),
5.46 (m, 1 H), 6.97 (s, 1 H), 7.13–7.23 (m, 2 H), 7.36 (d, J = 7.8 Hz,
1 H), 7.62 (d, J = 7.8 Hz, 1 H), 7.76 (br., 1 H) ppm.
3am: White solid. Yield: 133 mg, 80%. M.p. 61–62 °C. 1H NMR
(300 MHz, CDCl3): δ = 1.06 (s, 6 H), 2.37 (s, 4 H), 5.26 (d, J =
6.9 Hz, 1 H), 6.38 (d, J = 15.9 Hz, 1 H), 6.95 (dd, J = 6.9, 15.9 Hz,
1 H), 7.22–7.39 (m, 10 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
28.4, 31.99, 41.90, 60.52, 116.3, 126.4, 127.4, 127.8, 128.1, 128.5,
Supporting Information (see footnote on the first page of this arti-
cle): 1H NMR and 2D H–H NOESY NMR spectra for the mix-
tures of 3gf/3hf and 3gn/3hn.
129.0, 129.8, 130.6, 131.7, 137.3, 142.4 ppm. IR (KBr): ν = 3024,
˜
2957, 1598, 1376, 1256, 746, 696 cm–1. MS (ESI): m/z (%) = 331
(100) [M – H]–. C23H24O2 (332.18): calcd. C 83.10, H 7.28; found
C 82.92, H 7.33.
Acknowledgments
3an:[11a] White solid. Yield: 131 mg, 90%. M.p. 84–85 °C. 1H NMR
(300 MHz, CDCl3): δ = 1.92 (s, 3 H), 2.25 (s, 3 H), 4.34 (m, 2 H),
6.17 (dd, J = 5.7, 15.9 Hz, 1 H), 6.48 (d, J = 15.9 Hz, 1 H), 7.22–
7.34 (m, 10 H) ppm.
We gratefully acknowledge the National Natural Science Founda-
tion of China (20672053, 20832001) and the National Basic Re-
search Program of China (2007CB925103) for their financial sup-
port. The Program for New Century Excellent Talents in the Uni-
versity of China (NCET-06-0425) is also acknowledged.
3bn:[11a] Yellow oil. Yield: 72 mg, 63%. 1H NMR (300 MHz,
CDCl3): δ = 1.09 (d, J = 6.9 Hz, 3 H), 2.14 (s, 3 H), 2.24 (s, 3 H),
3.20–3.26 (m, 1 H), 3.70 (d, J = 10.5 Hz, 1 H), 6.00 (dd, J = 15.9,
8.7 Hz, 1 H), 6.45 (d, J = 15.9 Hz, 1 H), 7.22–7.32 (m, 5 H) ppm.
[1] For reviews, see: a) B. M. Trost, M. L. Crawley, Chem. Rev.
2003, 103, 2921–2944; b) B. M. Trost, J. Org. Chem. 2004, 69,
5813–5837; c) O. Belda, C. Moberg, Acc. Chem. Res. 2004, 37,
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T. Takehana, T. Ishihara, H. Yamanaka, Org. Biomol. Chem.
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Innovations in Organic Synthesis, Wiley, New York, 1995; b)
B. M. Trost, D. L. Van vranken, Chem. Rev. 1996, 96, 395–422;
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Catalysis (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto),
Springer, Berlin, 1999, vol. 2, ch. 24.
[4] To the best of our knowledge, strong base is still inevitable for
most cases, but recently, progress in direct substitution of allylic
alcohols has been reported. For direct substitution catalyzed
by Pd without additive, see: a) F. Ozawa, H. Okamoto, S. Ka-
wagishi, S. Yamamoto, T. Minami, M. Yoshifuji, J. Am. Chem.
Soc. 2002, 124, 10968–10969; b) Y. Kayaki, T. Koda, T. Ikariya,
J. Org. Chem. 2004, 69, 2595–2597; for direct substitution cata-
lyzed by Pd with additive, see: c) K. Manabe, S. Kobayashi,
Org. Lett. 2003, 5, 3241–3244; d) K.-H. Gan, C.-J. Jhong, S.-
C. Yang, Tetrahedron 2008, 64, 1204–1212; e) H. Tsukamoto,
M. Sato, Y. Kondo, Chem. Commun. 2004, 1200–1201; f) S.-C.
Yang, Y.-C. Hsu, K.-H. Gan, Tetrahedron 2006, 62, 3949–3958;
for direct substitution catalyzed by Rh, see: g) G. W. Kabalka,
G. Dong, B. Venkataiah, Org. Lett. 2003, 5, 893–895.
[5] a) M. Yasuda, T. Somyo, A. Baba, Angew. Chem. Int. Ed. 2006,
45, 793–796; b) P. R. Krishna, E. R. Sekhar, Y. L. Prapurna,
Tetrahedron Lett. 2007, 48, 9048–9050; for InBr3 as catalyst,
see: c) J. S. Yadav, B. V. Subba Reddy, S. Aravind, G. G. K. S.
Narayana Kumar, A. Srinivas Reddy, Tetrahedron Lett. 2007,
48, 6117–6120.
3cn:[29] Yellow oil (keto/enol, 1:0.92). Yield: 62 mg, 57%. 1H NMR
(300 MHz, CDCl3): δ = 2.17 (s, 6 H, enol), 2.22 (s, 6 H, keto), 2.76
(td, J = 6.9, 0.9 Hz, 2 H, keto), 3.17 (dd, J = 5.4, 1.5 Hz, 2 H,
enol), 3.81 (t, J = 6.9 Hz, 1 H, keto), 6.08 (dt, J = 15.9, 7.2 Hz, 1
H, keto), 6.22 (dt, J = 15.9, 5.4 Hz, 1 H, enol), 6.36 (d, J = 15.9 Hz,
1 H, enol), 6.46 (d, J = 15.9 Hz, 1 H, keto), 7.21–7.34 (m, 10 H,
keto + enol) ppm.
3ao:[11a] Colorless oil (mixture of diastereoisomers, ca. 3:2). Yield:
156 mg, 97%. 1H NMR (300 MHz, CDCl3): δ = 0.98 (t, J = 6.9 Hz,
1.2 H, diast. A), 1.22 (t, J = 6.9 Hz, 1.8 H, diast. B), 2.06 (s, 1.8
H, diast. B), 2.33 (s, 1.2 H, diast. A), 3.95 (q, J = 6.9 Hz, 0.8 H,
diast. A), 4.10–4.23 (m, 2 H), 4.31–4.40 (m, 1.2 H, diast. B), 6.29
(m, 1 H), 6.43 (m, 1 H), 7.24–7.32 (m, 10 H) ppm.
3ap:[30] Pale-yellow oil. Yield: 98 mg, 78%. 1H NMR (300 MHz,
CDCl3): δ = 2.10 (s, 3 H), 2.94 (m, 2 H), 4.07 (q, J = 6.3 Hz, 1 H),
6.35 (m, 2 H), 7.19–7.33 (m, 10 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 31.1, 44.4, 49.8, 126.6, 127.1, 127.7, 128.0, 128.9,
129.1, 130.4, 132.8, 137.5, 143.4, 207.3 ppm. IR (KBr): ν = 3420,
˜
1715, 1599, 1493, 1450, 1414, 1358, 1158, 966, 745, 697, 540 cm–1.
3aq:[21] Colorless oil (mixture of diastereoisomers, ca. 1:1). Yield:
94 mg, 65%. 1H NMR (300 MHz, CDCl3): δ = 1.57 (m, 4 H), 1.90
(m, 2 H), 2.35 (m, 2 H), 2.86 (m, 1 H), 3.87 (dd, J = 9.0, 8.7 Hz,
0.5 H, diast. A), 3.97 (dd, J = 9.0, 8.7 Hz, 0.5 H, diast. B), 6.26–
6.34 (m, 1 H), 6.43–6.48 (m, 1 H), 7.15–7.43 (m, 10 H) ppm.
1
3gf and 3hf: Colorless oil (3gf/3hf, 54:46). Data for 3gf: H NMR
(300 MHz, CDCl3): δ = 3.40 (s, 3 H), 3.81 (s, 3 H), 4.77–4.81 (m,
1 H), 6.17 (dd, J = 7.2, 15.9 Hz, 1 H), 6.59 (d, J = 15.6 Hz, 1 H),
1
6.86 (d, J = 9 Hz, 2 H), 7.24–7.42 (m, 7 H) ppm. Data for 3hf: H
NMR (300 MHz, CDCl3): δ = 3.38 (s, 3 H), 3.83 (s, 3 H), 4.77–
4.81 (m, 1 H), 6.32 (dd, J = 7.2, 15.9 Hz, 1 H), 6.63 (d, J = 15.6 Hz,
1 H), 6.93(d, J = 9 Hz, 2 H), 7.24–7.42 (m, 7 H) ppm. Data for the
mixture: 13C NMR (75 MHz, CDCl3): δ = 55.7, 56.7, 56.8, 84.3,
[6] a) U. Jana, S. Maiti, S. Biswas, Tetrahedron Lett. 2007, 48,
7160–7163; b) U. Jana, S. Biswas, S. Maiti, Tetrahedron Lett.
Eur. J. Org. Chem. 2009, 666–672
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