836
C. D. Roy
Regioselective Cleavage of ( )-(2,3-Epoxypropyl)benzene
with Dimethoxyboron Chloride
[7] B. Das, M. Krishnaiah, K. Venkateswarlu, Tetrahedron Lett.
2006, 47, 4457, and references therein. doi:10.1016/J.TETLET.
2006.04.059
[8] (a) M. V. Bhatt, S. U. Kulkarni, Synthesis 1983, 249, and refer-
ences therein. doi:10.1055/S-1983-30301
(b)A. K. Mandal, N. R. Soni, K. R. Ratnam, Synthesis 1985, 274.
doi:10.1055/S-1985-31174
[9] (a) M. V. Bhatt, J. Organomet. Chem. 1978, 156, 221.
doi:10.1016/S0022-328X(00)84879-2
To
a cooled stirred solution of (MeO)2BCl (6.0 mmol) in
n-pentane/CH2Cl2 (19–20 mL) at −78◦C under nitrogen atmosphere,
was added ( )-(2,3-epoxypropyl)benzene (5.0 mmol) via syringe. The
resulting reaction mixture was stirred at −78◦C for 3.5 h, and then
treated with water (15 mL). The organic layer was separated and the
aqueous layer was extracted with CH2Cl2 (3 × 25 mL), the combined
organic extracts were dried (Na2SO4), filtered, and evaporated to dry-
ness in vacuo.The regioselectivity was determined using 1H NMR spec-
troscopic data by either integrating and comparing the protons attached
to –OH or –Br present in both regioisomers (96:04). The chemical yield
(90%) was determined by 1H NMR spectroscopy using biphenyl as an
internal standard. Finally the major regioisomer was purified on sil-
ica gel column and characterized by 1H and 13C NMR spectroscopic
data. 1-Chlorododecan-2-ol,[11b] 2-chlorododecan-1-ol,[11b] 2-chloro-
1-phenylethanol,[11b] 2-chloro-2-phenylethanol,[11b] and 1-chloro-3-
phenoxypropan-2-ol[11c] are well characterized.
(b) S. U. Kulkarni, V. D. Patil, Heterocycles 1982, 18, 163.
(c) N. N. Joshi, M. Srebnik, H. C. Brown, J.Am. Chem. Soc. 1988,
110, 6246. doi:10.1021/JA00226A050
(d) M. Srebnik, N. N. Joshi, H. C. Brown, Isr. J. Chem. 1989,
29, 229.
(e) H. C. Brown, C. D. Roy, Mol. Online 1998, 2, 114.
doi:10.1007/S007830050066
(f) C. D. Roy, H. C. Brown, Tetrahedron Asymmetry 2006, 17,
1931, andreferencestherein. doi:10.1016/J.TETASY.2006.06.044
(g) C. D. Roy, H. C. Brown, J. Chem. Res. 2006, 639.
[10] (a)Y. Guindon, C.Yoakim, H. E. Morton, Tetrahedron Lett. 1983,
24, 2969. doi:10.1016/S0040-4039(00)88071-5
1-Chloro-3-phenylpropan-2-ol: δH (CDCl3) 7.40–7.10 (5H, m,
ArH), 4.00 (1H, m, CHOH), 3.70–3.40 (2H, ddd, CH2Cl), 2.88 (2H, d,
ArCH2), 2.22 (1H, d, CHOH). δC (CDCl3) 136.9 (ArC1), 129.3 (ArC3,
C5), 128.7 (ArC2, C6), 126.8 (ArC4), 72.2 (C2), 49.1 (C1), 40.6 (C3).
1-Chloro-3-isopropoxypropan-2-ol: δH (CDCl3) 3.90 (1H, m,
CHOH), 3.70 (3H, m, CHO and CH2O), 3.50 (2H, d, CH2Cl), 2.65
(1H, d, OH), 1.17 (6H, d, (CH3)2CH). δC (CDCl3) 72.4 (C2), 70.4 (C3),
68.6 (C4), 45.9 (C1), 22.0 (C5), 21.9 (C6).
1-Chloro-3-(1,1,2,2-tetrafluoroethoxy)propan-2-ol: δH (CDCl3)
6.00–5.50 (1H, m, CHF2), 4.10 (3H, m, CHO and CH2O), 3.66 (2H,
m, CH2Cl), 2.42 (1H, d, OH). δC (CDCl3) 117.2 (C4), 107.6 (C5), 69.2
(C2), 64.7 (C3), 45.4 (C1).
(b) Y. Guindon, M. Therien, Y. Girard, C. Yoakim, J. Org.
Chem. 1987, 52, 1680, and references therein. doi:10.1021/
JO00385A007
[11] (a) P. Bovicelli, E. Mincione, G. Ortaggi, Tetrahedron Lett. 1991,
32, 3719. doi:10.1016/S0040-4039(00)79777-2
(b) C. E. Garrett, G. C. Fu, J. Org. Chem. 1997, 62, 4534.
doi:10.1021/JO970419G
(c) H. Kotsuki, T. Shimanouchi, R. Ohshima, S. Fujiwara, Tetra-
hedron 1998, 54, 2709. doi:10.1016/S0040-4020(98)83007-X
(d) S. E. Denmark, P. A. Barsanti, K. T. Wong, R. A. Stavenger,
J. Org. Chem. 1998, 63, 2428. doi:10.1021/JO9801420
(e) J. M. Ready, E. N. Jacobsen, J. Am. Chem. Soc. 1999, 121,
6086. doi:10.1021/JA9910917
(f) S. Reymond, J. M. Brunel, G. Buono, Tetrahedron Asymmetry
2000, 11, 4441. doi:10.1016/S0957-4166(00)00432-8
(g) G. Sabitha, R. S. Babu, M. Rajkumar, Ch. S. Reddy,
J. S. Jadav, Tetrahedron Lett. 2001, 42, 3955. doi:10.1016/S0040-
4039(01)00622-0
Acknowledgments
Financial supports from the Purdue Borane Research Fund
and the H. C. Brown Center for Borane Research are greatly
appreciated.
References
(h) F. Sartillo-Piscil, L. Quintero, C. Villegas, E. S. Juarez,
C.A. Parrodi,Tetrahedron Lett. 2002, 43, 15. doi:10.1016/S0040-
4039(01)02088-3
(i) L. S. Wang, T. K. Hollis, Org. Lett. 2003, 5, 2543.
doi:10.1021/OL034816R
(j) Y. Tomata, M. Sasaki, K. Tanino, M. Miyashita, Tetrahedron
Lett. 2003, 44, 8975. doi:10.1016/J.TETLET.2003.10.001
(k) L. W. Xu, L. Li, C. G. Xia, P. Q. Zhao, Tetrahedron Lett. 2004,
45, 2435. doi:10.1016/J.TETLET.2004.01.042
(l) A. McCluskey, S. K. Leitch, J. Garner, C. E. Caden, T. A. Hill,
L. R. Odell, S. G. Stewart, Tetrahedron Lett. 2005, 46, 8229.
doi:10.1016/J.TETLET.2005.09.088
[1] (a) D. J. Faulkner, Nat. Prod. Rep. 1984, 251. doi:10.1039/
NP9840100251
(b) D. J. Faulkner, Nat. Prod. Rep. 1986, 1. doi:10.1039/
NP9860300001
[2] (a) C. Bonini, G. Righi, Synthesis 1994, 225, and references
therein. doi:10.1055/S-1994-25445
(b) I. Shibata, A. Baba, H. Matsuda, Tetrahedron Lett. 1986, 27,
3021. doi:10.1016/S0040-4039(00)84706-1
(c) J. Iqbal, M. A. Khan, R. R. Srivastava, Tetrahedron Lett. 1988,
29, 4985. doi:10.1016/S0040-4039(00)80659-0
(d) J. A. Ciaccio, K. J. Adess, T. W. Bell, Tetrahedron Lett. 1986,
27, 3697. doi:10.1016/S0040-4039(00)83856-3
(e) M. Chini, P. Crotti, C. Gardelli, F. Macchia,Tetrahedron 1992,
48, 3805. doi:10.1016/S0040-4020(01)92271-9
(m) N. Iranpoor, H. Firouzabadi, R.Azadi, F. Ebrahimzadeh, Can.
J. Chem. 2006, 84, 69. doi:10.1139/V05-261
[12] R. B. Castle, D. S. Matteson, J. Organomet. Chem. 1969, 20,
19. During the preparation of this manuscript, we learnt that
Matteson’s group had earlier prepared dimethoxyboron chloride
and used in the synthesis of octamethyl methanetetraboronate,
[(MeO)2B]4C. doi:10.1016/S0022-328X(00)80082-0
[3] I. Cabanal-Duvillard, J. F. Berrier, J. Royer, H. P. Husson,Tetrahe-
dron Lett. 1998, 39, 5181. doi:10.1016/S0040-4039(98)01017-X
[4] M. Sefkow, M. Kiffe, G. Hofle, Bioorg. Med. Chem. Lett. 1998,
8, 3031. doi:10.1016/S0960-894X(98)00546-0
[5] R. C. Larock, Comprehensive Organic Transformations 1999,
pp. 1027–1045 (Wiley-VCH: New York, NY).
[6] B. C. Ranu, S. Banerjee, J. Org. Chem. 2005, 70, 4517, and
references therein. doi:10.1021/JO0500885