4
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
Schulz, J. S. Dickschat, ChemBioChem 2014, 15, 2379. (h) J. S.
Yadav, G. M. Reddy, S. R. Anjum, B. V. S. Reddy, Eur. J. Org.
Chem. 2014, 11, 4389. (i) S. Torijano-Gutierrez, C. Vilanova, S.
Diaz-Oltra, J. Murga, E. Falomir, M. Carda, J. A. Marco, Eur. J.
Org. Chem. 2014, 11, 2284. (j) J. Willwacher, A. Fürstner,
Angew. Chem. Int. Ed. 2014, 53, 4217. (k) M. Tokuda, Y.
Kurogome, R. Katoh, Y. Nohara, Y. Hattori, H. Makabe,
Tetrahedron Lett. 2014, 55, 4189.
T. Yamakawa, M. Takizawa, T. Ohnishi, H. Koyama, S. Shinoda,
Catal. Commun. 2001, 2, 191.
N. Kibino, Y. Kadowaki, M. Sakai, Y. Hetsugi, PCT Int. Appl.
WO 2005075392, A2, 2005.
1
2
3
4
5
6
7
8
9
methyl vinyl ketone (MVK) with ethanol 2a was performed
under the optimized reaction conditions at 40oC (same as
1
entry 6 in Table 1), and H NMR analysis of the crude
product implied that the polymerization of MVK mainly
proceeded. Therefore, we considered that generation of
appropriate
amount
of
α,β-unsaturated
carbonyl
intermediate II through the borrowing hydrogen process is
important for the successful formation of the corresponding
γ-alkoxy alcohols IV, in which consumption of reactive
4
5
6
10 intermediate II by polymerization would be suppressed.
11 In summary, ruthenium catalysis for the
Several reactions on the basis of borrowing hydrogen: (a) C.
Lofberg, R. Grigg, M. A. Whittaker, A. Keep, A. Derrick, J. Org.
Chem. 2006, 71, 8023; (b) C. Lofberg, R. Grigg, A. Keep, A.
Derrick, V. Sridharan, C. Kilner, Chem. Commun. 2006, 5000.
a
12 hydroalkoxylation of allylic alcohols was developed. The
13 reaction tolerated several combinations of allylic alcohols
14 including methoxyethanol and amino alcohols and provided
15 the corresponding γ-alkoxypropanols in good yield under
16 mild reaction conditions.
(c) P. A. Slatfor, M. K. Whittlesey, J. M.
J Williams,
Tetrahedron Lett. 2006, 47, 6787. (d) K. Fujita, T. Fujii, R.
Yamaguchi, Org. Lett. 2004, 6, 3525. (e) Y. Watanabe, Y. Tsuji,
H. Ige, Y. Ohsugi, T. Ohta, J. Org. Chem. 1984, 49, 3359. (f) Y.
Nakamura, T. Ohta, Y. Oe, Chem. Commun. 2015, 51, 7459.
(a) B. M. Trost, R. J. Kulawiec, J. Am. Chem. Soc. 1993, 115,
2027. (b) E. Bouwman, R. C. van der Drift, E. Drent, J.
Organomet. Chem. 2002, 650, 1. (c) R. Uma, M. K. Davies, C.
Crévisy, R. Grée, Eur. J. Org. Chem. 2001, 3141.
(a) V. Cadierno, J. Francos, J. Gimeno, N. Nebra, Chem.
Commun. 2007, 2536. (b) V. Cadierno, P. Crochet, J. Francos, S.
E. García-Garrido, J. Gimeno, N. Nebra, Green Chem. 2009, 11,
1992–2000.
(a) Y. Oe, Y. Uozumi, Synlett, 2011, 6, 787. (b) D. Cuperly, J.
Petrignet, C. Crevisy, R. Grée, Chem. Eur. J. 2006, 12, 3261. (c)
X. -F. Yang, M. Wang, R. S. Varma, C. -J. Li, J. Mol. Catal. A
2004, 214, 147. (d) X. -F. Yang, M. Wang, R. S. Varma, C. -J. Li,
Org. Lett. 2003, 5, 657. (e) M. Wang, C. -J. Li, Tetrahedron Lett.
2002, 43, 3589.
17
18 Supporting
19 http://dx.doi.org/10.1246/cl.******.
Information
is
available
on
7
8
9
20 References and Notes
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
1
For recent examples of Williamson etherification for the
construction of 3-alkoxypropan-1-ols in total syntheses, see: (a)
E. Brun, V. Bellosta, J. Cossy, J. Org. Chem. 2016, 81, 8206. (b)
J. N. Kumar, B. Das, RSC Adv. 2015, 5, 14465. (c) C. N. Reddy,
Q. Ye, S. Chourey, S. Gravel, W. S. Powell, J. Rokach,
Tetrahedron Lett. 2015, 56, 6896. (d) A. Wadood, H. Kim, C. M.
Park, J. -H. Song, S. Lee, Arch. Pharm. Res. 2015, 38, 2029. (e)
E. Brun, V. Bellosta, J. Cossy, J. Org. Chem. 2015, 80, 8668. (f)
A. N. Purude, K. P. Pawar, N. B. Patil, U. R. Kalkote, S. P.
Chavan, Tetrahedron: Asymmetry 2015, 26, 281. (g) T. Sato, H.
Ueda, H. Tokuyama, Tetrahedron Lett. 2014, 55, 7177. (h) H.
Peifer, R. Berger, V. W. Shurtleff, J. C. Conrad, D. W. C.
MacMillan, J. Am. Chem. Soc. 2014, 136, 5900. (i) M.
Kretschmer, M. Dieckmann, P. Li, S. Rudolph, D. Herkommer,
J. Troendlin, D. Menche, Chem. Eur. J. 2013, 19, 15993. (j) B.
Nagaiah, A. V. Narsaiah, Helv. Chim. Acta. 2013, 96, 1948. (k) J.
S. Villadsen, H. M. Stephansen, A. R. Maolanon, P. Harris, C. A.
Olsen, J. Med. Chem. 2013, 56, 6512.
101 10 (a) K. Hiraki, T. Matsunaga, H. Kawano, Organometalics 1994,
102
103
104
105
106
107
13, 1878. (b) N. Kuznik, S. Krompiec, T. Bieg, S. Baj, K. Skutil
A. Chrobok, J. Organomet. Chem. 2003, 665, 167. (c) T. Doi, T.
Fukuyama, S. Minamino, G. Husson, I. Ryu, Chem. Commun.
2006, 1875. (d) A. Denichoux, T. Fukuyama, T. Doi, J.
Horiguchi, I. Ryu, Org. Lett. 2010, 12, 1. (e) F. Perez, S. Oda, L.
M. Geary, M. J. Krische, Top. Curr. Chem. 2016, 374, 365.
108 11 For reviews see: (a) M. H. S. A. Hamid, P. A. Slatford, J. M. J.
109
110
Williams, Adv. Synth. Catal. 2007, 349, 1555. (b) G. Guillena, D.
J. Ramón, M. Yus, Chem. Rev. 2010, 110, 1611.
2
For recent examples of hydroboration/oxidation reactions for the
construction of 3-alkoxypropan-1-ols in total syntheses, see: (a)
A. Brinkø, M. T. Larsen, H. Koldsø, L. Besenbacher, A. Kolind,
B. Schiøtt, S. Sinning, H. H. Jensen, Bioorg. Med. Chem. 2016,
24, 2725. (b) D. Zurwerra, F. Glaus, L. Betschart, J. Schuster, J.
Gertsch, W. Ganci K. H. Altmann, Chem. Eur. J. 2012, 18,
16868. (c) B. Seetharamsingh, P. R. Rajamohanan, D. S. Reddy,
Org. Lett. 2015, 17, 1652. (d) X. Liang, M. K. Sen, J. –A. Jee, O.
Gelman, J. E. Marine, K. Kan, M. K. Endoh, D. A. Barkley, T.
Koga, J. G. Rudick, J. Polym. Sci. Part A: Polym. Chem. 2014,
52, 3221. (e) T. E. T. Pompeu, F. R. S. Alves, C. D. M.
Figueiredo, C. B. Antonio, V. Herzfeldt, B. C. Moura, S. M. K.
Rates, E. J. Barreiro, C. A. M. Fraga, F. Noël, Eur. J. Med. Chem.
2013, 66, 122. (f) A. Belaissaoui, I. M. Saez, S. J. Cowling, J. W.
Goodby, Macromolecules 2013, 46, 1268.
3
For recent examples of 1,2-addition of organometallic
compounds for the construction of 3-alkoxypropan-1-ols in total
syntheses, see: (a) K. Ochiai, S. Kuppusamy, Y. Yasui, K.
Harada, N. R. Gupta, Y. Takahashi, T. Kubota, J. Kobayashi, Y.
Hayashi, Chem. Eur. J. 2016, 22, 3287. (b) T. Itagaki, A.
Kawamata, M. Takeuchi, K. Hamada, Y. Iwabuchi, T. Eguchi, F.
Kudo, T. Usui, N. Kanoh, J. Antibiot. 2016, 69, 287. (c) S.
Bujaranipalli, S. Das, Tetrahedron: Asymmetry 2016, 27, 254. (d)
E. Sato, Y. Tanabe, N. Nakajima, A. Ohkubo, K. Suenaga, Org.
Lett. 2016, 18, 2047. (e) J. S. Yadav, P. Dutta, J. Org. Chem.
2016, 81, 1786. (f) J. Willwacher, B. Heggen, C. Wirtz, W. Thiel,
A. Fürstner, Chem. Eur. J. 2015, 21, 10416. (g) L. Barra, B.