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DOI: 10.1055/s-2008-1042928
Unexpected Lewis Acid Mediated Reactions of 1-Arylbut-3-en-1-ols with Trimethyl Orthoformate - A New Synthesis of Homoallyl Ethers and Chlorides
Publication History
Publication Date:
11 March 2008 (online)
Abstract
1-Arylbut-3-en-1-ols react with trimethyl orthoformate in the presence of Lewis acids like InCl3, BiCl3, TiCl4, or BF3·OEt2 providing homoallyl ethers or homoallyl chlorides in high yields.
Key words
alcohols - ethers - indium - halides - Lewis acids
- 1
Pindur U. The Chemistry of Acid Derivatives, In The Chemistry of Functional Groups Suppl. B, Part 2, Vol. 2: Wiley; New York: 1992. p.967 - 2
Perron F.Gahman TC.Albizati KF. Tetrahedron Lett. 1988, 29: 2023 -
3a
Perron F.Albizati KF. J. Org. Chem. 1987, 52: 4128 -
3b
Perron-Sierra F.Promo MA.Martin VA.Albizati KF. J. Org. Chem. 1991, 56: 6188 - 4
Pindur U.Müller J.Flo C.Witzel H. Chem. Soc. Rev. 1987, 16: 75 - For examples, see:
-
5a
Keck GE.Covel JA.Schiff T.Yu T. Org. Lett. 2002, 4: 1189 -
5b
Mekhalfia A.Markó IE.Adams H. Tetrahedron Lett. 1991, 32: 4783 -
5c
Martin VA.Perron F.Albizati KF. Tetrahedron Lett. 1990, 31: 301 - 6 For a review, see:
Clarke PA.Santos S. Eur. J. Org. Chem. 2006, 2045 -
7a
Kopecky DJ.Rychnovsky SD. J. Am. Chem. Soc. 2001, 123: 8420 -
7b
Balado CP.Markó IE. Tetrahedron Lett. 2005, 46: 4887 -
7c
Leroy B.Markó IE. J. Org. Chem. 2002, 67: 8744 -
7d
Markó IE.Mekhalfia A. Tetrahedron Lett. 1992, 33: 1799 -
7e
Mekhalfia A.Markó IE.Adams H. Tetrahedron Lett. 1991, 32: 4783 -
7f
Wei ZY.Wang D.Li JS.Chan TH. J. Org. Chem. 1989, 54: 5768 -
8a
Schmidt D.Leutbecher H.Conrad J.Klaiber I.Mika S.Greiner G.Beifuss U. Synlett 2007, 1725 -
8b
Leutbecher H.Schmidt D.Conrad J.Beifuss U. Synlett 2007, 2545 - 9
Ropp GA.Coyner EC. J. Am. Chem. Soc. 1950, 72: 3960 -
10a
Dobbs AP.Pivnevi L.Penny MJ.Martinović S.Iley JN.Stephenson PT. Chem. Commun. 2006, 3134 -
10b
Yang X.-F.Mague JT.Li C.-J. J. Org. Chem. 2001, 66: 739 - 12
Yamamoto Y.Asao N. Chem. Rev. 1993, 93: 2207 -
13a
Hosomi A.Endo M.Sakurai H. Chem. Lett. 1976, 941 -
13b
Hosomi A.Endo M.Sakurai H. Chem. Lett. 1978, 499 -
13c
Tsunoda T.Suzuki M.Noyori R. Tetrahedron Lett. 1980, 21: 71 -
13d
Sakurai H.Sasaki K.Hosomi A. Tetrahedron Lett. 1981, 22: 745 -
13e
Mukaiyama T.Nagaoka H.Murakami M.Ohshima M. Chem. Lett. 1985, 977 -
13f
Kawai M.Onaka M.Izumi Y. Chem. Lett. 1986, 381 -
13g
Tanaka H.Yamashita S.Ikemoto Y.Torii S. Tetrahedron Lett. 1988, 29: 1721 -
13h
Trehan A.Vij A.Walia M.Kaur G.Verma RD.Trehan S. Tetrahedron Lett. 1993, 34: 7335 -
13i
Hollis TK.Robinson NP.Whelan J.Bosnich B. Tetrahedron Lett. 1993, 34: 4309 -
13j
Komatsu N.Uda M.Suzuki H.Takahashi T.Domae T.Wada M. Tetrahedron Lett. 1997, 38: 7215 -
13k
Ishii A.Kotera O.Saeki T.Mikami K. Synlett 1997, 1145 -
13l
Yadav JS.Reddy BVS.Srihari P. Synlett 2001, 673 -
13m
Wieland LC.Zerth HM.Mohan RS. Tetrahedron Lett. 2002, 43: 4597 -
13n
Zerth HM.Leonard NM.Mohan RS. Org. Lett. 2003, 5: 55 - 14
Hunter R.Michael JP.Tomlinson GD. Tetrahedron 1994, 50: 871 - 15
Onishi Y.Ito T.Yasuda M.Baba A. Eur. J. Org. Chem. 2002, 1578
References and Notes
Similar results were obtained when 1a was reacted with triethyl orthoformate (TEOF).
16
General Procedure for InCl
3
-Mediated Reactions of Homoallyl Alcohols 1 with TMOF (2)
InCl3 (3 mmol) was added to a stirred solution of homoallyl alcohol 1 (3 mmol) and TMOF (2, 3 mmol) in CH2Cl2 (25 mL). The reaction mixture was stirred at r.t. under Ar until 1 had been completely consumed (TLC). Then H2O (25 mL) was added and the resulting mixture was extracted with CH2Cl2 (75 mL). The extracts were washed with brine (25 mL), dried over MgSO4, filtered and concentrated in vacuo. The products were purified by Kugelrohr distillation or flash chromatography on silica gel.
Selected data for 3e: R f = 0.20 (PE-CH2Cl2, 7:3). UV/Vis (MeCN): λmax (log ε) = 269 (3.17), 277 (3.18) nm. IR (ATR): 3090, 2927, 2819, 1641 (C=C), 1500, 1448, 1357, 1189, 1156, 1108 (C-O-C), 1091, 974, 912, 808, 729 cm-1. 1H NMR (300 MHz, CDCl3): δ = 2.33 (s, 3 H, 2′-CH3), 2.38 (s, 3 H, 5′-CH3), 2.44 (br ddd, 1 H, ² J gem = 14.5 Hz, ³ J = ca. 7.4 Hz, ³ J = ca. 7.4 Hz, 2-H), 2.53 (br ddd, 1 H, ² J gem = 14.5 Hz, ³ J = ca. 7.0 Hz, ³ J = ca. 7.0 Hz, 2-H), 3.27 (s, 3 H, 1-OCH3), 4.48 (br dd, ³ J = 7.9 Hz, ³ J = 8.0 Hz, 1 H, 1-H), 5.11 (ddt, 1 H, ³ J cis = 9.8 Hz, ² J = 1.3 Hz, 4-H), 5.17 (dq, 1 H, ³ J trans = 17.2 Hz, ² J = 1.3 Hz, 4-H), 5.87 (dddd, 1 H, ³ J cis = 10.1, ³ J trans = 17.1 Hz, ³ J = ca. 7.0 Hz, ³ J = ca. 7.0 Hz, 3-H), 7.04 (br d, 3 J = 7.5 Hz, 1 H, 3′-H), 7.08 (br d, 3 J = 7.8 Hz, 1 H, 4′-H), 7.24 (s, 1 H, 6-H). 13C NMR (75 MHz, CDCl3): δ = 18.7 (2′-CH3), 21.1 (5′-CH3), 41.6 (C-2), 56.6 (1-OCH3), 80.0 (C-1), 116.6 (C-4), 126.4 (C-6′), 127.8 (C-4′), 130.2 (C-3′), 132.2 (C-1′), 135.2 (C-3), 135.6 (C-5′), 139.5 (C-1′). MS (EI, 70 eV): m/z (%) = 149 (100) [M+ - 41], 143 (12), 133 (45), 119 (59), 105 (65), 103 (15), 91 (31), 77 (32), 65 (8), 51 (10). HRMS (EI): m/z calcd for C13H18O: 190.1357; found: 190.1316 [M+]. Anal. Calcd for C13H18O: C, 82.06; H, 9.53. Found: C, 82.05; H, 9.58.
18Selected data for 4f: R f = 0.62 (PE-CH2Cl2, 7:3). UV/Vis (MeCN): λmax (log ε) = 271 (3.01), 265 (3.05) nm. IR (ATR): 3077, 2980, 2905, 1641 (C=C), 1604, 1508, 1431, 1343, 1295, 1220, 1156, 1073 (C-O-C), 1013, 991, 915, 831, 785, 722 cm-1. MS (EI, 70 eV): m/z (%) = 273 (4) [M+ - 41], 150 (20), 149 (100), 109 (35), 95 (3), 53 (2). HRMS (EI): m/z calcd for the fragment [C10H10F+]: 149.0761; found: 149.0750.
19Selected data for 5j: R f = 0.50 (PE). UV/Vis (MeCN): λmax (log ε) = 266 (1.97) nm. IR (ATR): 3080, 2980, 1654 (C=C), 1523, 1501, 1449, 1424, 1359, 1316, 1148, 1130, 1042, 991, 955, 928, 802, 761, 741, 684 cm-1. 1H NMR (500 MHz, CDCl3): δ = 2.96 (br ddd, 1 H, ² J = 14.3 Hz, ³ J = ca. 7.8 Hz, ³ J = ca. 7.8 Hz, 2-H), 3.05 (br ddd, 1 H, ² J = 14.3 Hz, ³ J = ca. 7.1 Hz, ³ J = ca. 7.1 Hz, 2-H), 5.15 (ddt, 1 H, ³ J = 10.1 Hz, ² J = 1.4 Hz, 4 J = 1.2 Hz, 4-H), 5.19 (dq, 1 H, ² J = 1.4 Hz, ³ J trans = 17.1 Hz, 4-H), 5.22 (br dd, 1 H, ³ J = ca. 8.0 Hz, ³ J = ca. 8.0 Hz, 1-H), 5.73 (dddd, 1 H, ³ J trans = 17.2 Hz, ³ J cis = 10.1 Hz, ³ J = ca. 7.0 Hz, ³ J = ca. 7.0 Hz, 3-H). 13C NMR (125 MHz, CDCl3): δ = 41.1 (C-2), 49.5 (C-1), 114.5 (C-1′), 119.5 (C-4), 132.5 (C-3) 138.7 (d, C-4′), 141.2 (d, C-3′and C-5′), 144.75 (d, C-2′and C-6′). MS (EI, 70 eV): m/z (%) = 256 (33) [M+], 215 (100) [M+ - 41], 207 (57), 194 (35), 181 (45), 151 (12), 143 (11), 123 (7), 105 (3), 99 (6), 75 (5), 51 (5). HRMS (EI): m/z calcd for C10H6ClF5: 256.0078; found: 256.0076 [M+].
20Compound 4f (D1): 1H NMR (500 MHz, CDCl3): δ = 2.34 (dddq, 1 H,
²
J = 13.9 Hz,
³
J = ca. 6.5 Hz,
³
J = ca. 6.5 Hz,
4
J = 1.1 Hz, 2-H), 2.55 (br dddt, 1 H,
²
J = 14.0 Hz,
³
J = ca. 7.2 Hz,
³
J = ca. 7.2 Hz,
4
J = 1.3 Hz, 2-H), 4.08 (dd, 1 H,
³
J = 7.3 Hz,
³
J = 6.6 Hz, 1-H), 4.96 (dddd, 1 H,
³
J
trans
= 17.2 Hz,
²
J = ca. 1.6 Hz,
4
J = ca. 1.6 Hz,
4
J = ca. 1.6 Hz, 4-H), 4.98 (br d, 1 H,
³
J
cis = 10.4 Hz, 4-H), 5.67 (dddd, 2 H,
³
J
trans
= 17.1 Hz,
³
J
cis
= 10.2 Hz,
³
J = ca. 6.9 Hz,
³
J = ca. 6.9 Hz, 3-H), 7.06 (br dd, 2 H,
³
J = 8.7 Hz,
³
J
H-F
= 8.0 Hz, 3′-H and 5′-H), 7.23 (br dd, 2 H,
³
J = 8.7 Hz,
4
J
H-F
= 5.5 Hz, 2′-H and 6′-H). 13C NMR (125 MHz, CDCl3): δ = 43.05 (C-2), 77.85 (C-1), 115.44 (d,
²
J
C-F
= 21.4 Hz, C-3′ and C-5′), 117.28 (C-4), 128.88 (d,
³
J
C-F
= 8.5 Hz, C-2′ and C-6′), 134.7 (C-3), 137.70 (d,
4
J
C-F
= 2.9 Hz, C-1′), 162.5 (d,
¹
J
C-F
= 245.5 Hz, C-4′).
Compound 4f (D2): 1H NMR (500 MHz, CDCl3): δ = 2.47 (dddq, 1 H,
²
J = 14.1 Hz,
³
J = ca. 7.1 Hz,
³
J = ca. 7.1 Hz,
4
J = 1.1 Hz, 2-H), 2.62 (dddt, 1 H,
²
J = 14.1 Hz,
³
J = ca. 7.1 Hz,
³
J = ca. 7.1 Hz,
4
J = 1.2 Hz, 2-H), 4.39 (dd, 1 H,
³
J = ca. 6.4 Hz,
³
J = ca. 6.4 Hz, 1-H), 5.04 (br d, 1 H,
³
J
cis
= 10.0 Hz, 4-H), 5.05 (dddd, 1 H,
³
J
trans
= 17.5 Hz,
²
J = ca. 1.6 Hz,
4
J = ca. 1.6 Hz,
²
J = ca. 1.6 Hz, 4-H), 5.77 (dddd, 2 H,
³
J
trans
= 16.9 Hz,
³
J
cis
= 10.5 Hz,
³
J = ca. 7.2 Hz,
³
J = ca. 7.2 Hz, 3-H), 6.94 (br dd, 2 H,
³
J = ca. 8.8 Hz,
³
J
H-F
= ca. 8.8 Hz, 3′-H and 5′-H), 7.14 (br dd, 2 H,
³
J = 8.6 Hz,
4
J
H-F
= 5.5 Hz, 2′-H and 6′-H). 13C NMR (125 MHz, CDCl3): δ = 41.96 (C-2), 79.4 (C-1), 115.06 (d,
²
J
C-F
= 21.3 Hz, C-3′and C-5′), 117.54 (C-4), 128.51 (d,
³
J
C-F
= 7.5 Hz, C-2′ and C-6′), 134.5 (C-3), 137.19 (d,
4
J
C-F
= 3.7 Hz, C-1′), 162.20 (d,
¹
J
C-F
= 244.7 Hz, C-4′).