Subscribe to RSS
DOI: 10.1055/s-0028-1087566
Combination of Lithium Chloride and Hexafluoroisopropanol for Friedel-Crafts Reactions
Publication History
Publication Date:
16 February 2009 (online)
Abstract
A combination of weak Lewis acid (LiCl) and weak Brønsted acid (hexafluoroisopropanol, HFIP) promotes efficiently the Friedel-Crafts reaction of electron-rich aromatic compounds with ethyl glyoxylate.
Key words
Friedel-Crafts reaction - glyoxylate - lithium chloride - hexafluoroisopropanol - Lewis acid - Brønsted acid
- 1
Olah GA.Krishnamurti R.Surya Prakash GK. Comprehensive Organic Synthesis Vol. 3:Trost BM.Fleming I. Pergamon; New York: 1991. p.293-339 - Selected examples:
-
2a
Kawada A.Mitamura S.Kobayashi S. Synlett 1994, 545 -
2b
Répichet S.Le Roux C.Dubac J.Desmurs J.-R. Eur. J. Org. Chem. 1998, 2743 -
2c
Kobayashi S.Komoto I. Tetrahedron 2000, 56: 6463 -
3a
Mine N.Fujiwara Y.Taniguchi H. Chem. Lett. 1986, 357 -
3b
Tsuchimoto T.Tobita K.Hiyama T.Fukuzawa S. J. Org. Chem. 1997, 62: 6997 -
3c
Shiina I.Suzuki M. Tetrahedron Lett. 2002, 43: 6391 -
3d
Noji M.Ohno T.Fuji K.Futaba N.Tajima H.Ishii K. J. Org. Chem. 2003, 68: 9340 -
3e
Mantri K.Komura K.Kubota Y.Sugi Y. J. Mol. Catal. A: Chem. 2005, 236: 168 -
3f
Jiang B.Huang ZG. Synthesis 2005, 2198 -
4a
Hao J.Taktak S.Aikawa K.Yusa Y.Hatano M.Mikami K. Synlett 2001, 1443 -
4b
Prakash GKS.Yan P.Török B.Olah GA. Synlett 2003, 527 -
4c
Ding H.Zhang HB.Chen YJ.Lu L.Wang D.Li CJ. Synlett 2004, 555 -
4d
Soueidan M.Collin J.Gil R. Tetrahedron Lett. 2006, 47: 5467 -
5a
Jiang B.Yang C.-G.Gu X.-H. Tetrahedron Lett. 2001, 42: 2545 -
5b
Zhao J.-L.Liu L.Zhang HB.Wu Y.-C.Wang D.Chen Y.-J. Tetrahedron Lett. 2006, 47: 2511 -
5c
Zhao J.-L.Liu L.Zhang HB.Wu Y.-C.Wang D.Chen Y.-J. Synlett 2006, 96 - Lewis acid catalysis:
-
6a
Bigi F.Casiraghi G.Casnati G.Sartori G.Fava GG.Belicchi MF. J. Org. Chem. 1985, 50: 5018 -
6b
Erker G.Van de Zeijden AAH. Angew Chem., Int. Ed. Engl. 1990, 29: 512 -
6c
Isshi A.Soloshonok VA.Mikami K. J. Org. Chem. 2000, 65: 1597 -
6d
Gathergood N.Zhuang W.Jørgensen KA.
J. Am. Chem. Soc. 2000, 122: 12517 -
6e
Zhuang W.Gathergood N.Hazell RG.Jørgensen KA. J. Org. Chem. 2001, 66: 1009 -
6f
Yuan Y.Wang X.Li X.Ding K. J. Org. Chem. 2004, 69: 146 -
6g
Zhao J.-L.Sui Y.Liu Y.-L.Wang D.Chen Y.-J. Org. Lett. 2006, 8: 6127 -
6h
Dong H.-M.Lu H.-H.Lu L.-Q.Chen C.-B.Xiao W.-J. Adv. Synth. Catal. 2007, 349: 1597 -
6i
Major J.Kwiatkowski Jurczak J. Org. Lett. 2008, 10: 2955 -
6j For a review, see:
Bandini M.Melloni A.Umani-Ronchi A. Angew. Chem. Int. Ed. 2004, 43: 550 - Organocatalysis:
-
7a
Török B.Abid M.London G.Esquibel J.Török M.Mhadgut SC.Yan P.Prakash GKS. Angew. Chem. Int. Ed. 2005, 44: 3086 -
7b
Li H.Wang Y.-Q.Deng L. Org. Lett. 2006, 8: 4063 -
7c
Zhao J.-L.Liu L.Gu C.-L.Wang D.Chen Y.-J. Tetrahedron Lett. 2008, 49: 1476 -
8a
Chen J.Chen X.Willot M.Zhu J. Angew. Chem. Int. Ed. 2006, 45: 8028 -
8b
Chen X.Zhu J. Angew. Chem. Int. Ed. 2007, 46: 3962 -
8c
Wu Y.-C.Liron M.Zhu J. J. Am. Chem. Soc. 2008, 130: 7148 -
8d For an excellent review, see:
Scott JD.Williams RM. Chem. Rev. 2002, 102: 1669 -
9a
De Paolis M.Chiaroni A.Zhu J. Chem. Commun. 2003, 2896 -
9b
Chen X.Chen J.De Paolis M.Zhu J. J. Org. Chem. 2005, 70: 4397 - 10
Chen J.Chen X.Bois-Choussy M.Zhu J. J. Am. Chem. Soc. 2006, 128: 87 - Selected recent references on HFIP-assisted transformations:
-
11a
Cativirla C.García JI.Majoral JA.Salvatella L. Can. J. Chem. 1994, 72: 308 -
11b
Ichikawa J.Miyazaki S.Fujiwara M.Minami T.
J. Org. Chem. 1995, 60: 2320 -
11c
Das U.Crousse B.Kesavan V.Bonnet-Delpon D.Bégué J.-P. J. Org. Chem. 2000, 65: 6749 -
11d
Takita R.Oshima T.Shibasaki M. Tetrahedron Lett. 2002, 43: 4661 -
11e
Neimann K.Neumann R. Org. Lett. 2000, 2: 2861 -
11f
Snider BB.O’Hare SM. Tetrahedron Lett. 2001, 42: 2455 -
11g
Johnston BD.Ghavami A.Jensen MT.Svensson B.Pinto BM. J. Am. Chem. Soc. 2002, 124: 8245 -
11h
Yagi H.Ramesha AR.Kalena G.Sayer JM.Kumar S.Jerina DM. J. Org. Chem. 2002, 67: 6678 -
11i
Canesi S.Bouchu D.Ciufolini MA. Org. Lett. 2005, 7: 175 -
11j For a review, see:
Bégué J.-P.Bonnet-Delpon D.Crousse B. Synlett 2004, 18 - Formation of bisindolylalkanes, see for examples:
-
13a
Gibbs TJK.Tomkinson NCO. Org. Biomol. Chem. 2005, 3: 4043 -
13b
Nair V.Abhilash KG.Vidya N. Org. Lett. 2005, 7: 5857 - 14
Schadt FL.Bentley TW.Schleyer P.v.R.. J. Am. Chem. Soc. 1976, 98: 7667 -
15a
Eberson L.Hartshorn MP.Persson O.Radner F. Chem. Commun. 1996, 2105 -
15b
Berkessel A.Adrio AA.Hüttenhain D.Neudörfl JM. J. Am. Chem. Soc. 2006, 128: 8421
References and Notes
Analytical Data
Compound 3b: IR (neat): 3428, 2904, 1734, 1654,
1499, 1461, 1370, 1215, 1046, 994, 931 cm-¹. ¹H
NMR (300 MHz, CDCl3, 293 K): δ = 6.54
(s, 1 H), 6.26 (br s, 1 H), 5.96 (d, J = 1.1
Hz, 1 H), 5.91 (d, J = 1.1
Hz, 1 H), 5.12 (s, 1 H), 5.05 (s, 2 H), 4.23 (dq, J = 10.2,
7.2 Hz, 1 H), 4.18 (dq, J = 10.2, 7.2
Hz, 1 H), 3.49 (s, 3 H), 1.43 (t, J = 7.2
Hz, 3 H) ppm.
¹³C NMR (75
MHz, CDCl3, 293 K): δ = 173.0,
142.3, 141.5, 134.4, 132.3, 110.7, 108.3, 102.1, 97.6, 68.3, 62.2,
56.5, 14.0 ppm. HRMS (ESI+): m/z [M + Na]+ calcd
for C13H16O8: 323.0743; found:
323.0745.
Compound 3c: IR (neat):
3386, 2930, 2857, 1731, 1482, 1335, 1251, 1126, 1006 cm-¹. ¹H
NMR (300 MHz, CDCl3, 293 K): δ (mixture of two
diastereomers) = 6.89 (2 s, 1 H), 6.55
(s, 1 H), 5.18 (d, J = 3.1
Hz, 1 H), 4.30 (dq, J = 10.7,
7.2 Hz, 1 H), 4.20 (dq, J = 10.7,
7.2 Hz, 1 H), 3.74 (s, 3 H), 3.45 (d, J = 3.1
Hz, 1 H), 2.15 (s, 3 H), 1.26 (t, J = 7.2
Hz, 3 H), 1.01 (s, 9 H), 0.96 (2 t, J = 7.6
Hz, 3 H), 0.72 (m, 2 H), 0.16 (s, 3 H) ppm. ¹³C
NMR (75 MHz, CDCl3, 293 K): δ = 173.2, 150.4,
148.1, 142.1, 120.9, 117.7, 117.1, 72.7, 62.6, 60.1, 26.3 (3 C),
18.8, 14.1, 9.2, 7.5, 4.8, -6.5 ppm. MS (ESI+):
m/z = 791.3 [2
M + Na]+, 407.1 [M + Na]+,
367.2 [M - H2O + H]+.
HRMS (ESI+): m/z [M + Na]+ calcd
for C19H32O6Si: 407.1866; found:
407.1862.
Compound 3d: IR (neat):
3349, 2983, 2903, 1722, 1628, 1485, 1442, 1169, 1033, 930 cm-¹. ¹H
NMR (500 MHz, CDCl3, 293 K): δ = 6.64
(s, 1 H), 6.42 (s, 1 H), 5.90 (s, 1 H), 5.89 (s, 1 H), 5.19 (s,
1 H), 4.28 (dq, J = 10.8,
7.1 Hz, 1 H), 4.21 (dq, J = 10.8,
7.1 Hz, 1 H), 1.25 (t, J = 7.1
Hz, 3 H) ppm. ¹³C NMR (75 MHz, CDCl3,
293 K): δ = 173.3, 150.4, 148.7,
141.5, 114.6, 107.8, 101.4, 99.8, 72.1, 62.7, 14.2 ppm. MS (ESI+): m/z = 263.0 [M + Na]+,
245.0 [M - H2O + Na]+, 223.1 [M - H2O + H]+.
HRMS (ESI+): m/z [M + Na]+ calcd for
C11H12O6: 263.0532; found: 263.0497.
Compound 3e: IR (neat): 3414, 2937, 2837, 1729,
1616, 1515, 1451, 1417, 1197, 1109, 997 cm-¹. ¹H
NMR (500 MHz, CDCl3, 293 K): δ = 7.21
(br s, 1 H), 6.67 (s, 1 H), 6.42 (s, 1 H), 5.22 (s, 1 H), 4.22 (dq, J = 10.8,
7.1 Hz, 1 H), 4.17 (dq, J = 10.8,
7.1 Hz, 1 H), 4.00 (s, 1 H), 3.79 (s, 3 H), 3.77 (s, 3 H), 1.21
(t, J = 7.1
Hz, 3 H) ppm. ¹³C NMR (75 MHz, CDCl3,
293 K): δ = 173.3, 150.2, 149.3,
142.7, 113.6, 111.9, 101.9, 71.8, 62.4, 56.6, 55.9, 14.1 ppm. MS
(ESI+): m/z = 279.1 [M + Na]+.
HRMS (ESI+): m/z [M + Na]+ calcd
for C12H16O6: 279.0845; found:
279.0840.
Compound 3f: IR (neat):
3418, 2961, 2871, 1724, 1625, 1460, 1368, 1222, 1059, 1024, 935
cm-¹. ¹H NMR (500 MHz,
CDCl3, 293 K): δ = 7.63
(br s, 1 H), 6.77 (d, J = 8.2 Hz,
1 H), 6.71 (d, J = 8.2
Hz, 1 H), 5.72 (br s, 1 H), 5.30 (s, 1 H), 4.33 (dq, J = 10.7,
7.1 Hz, 1 H), 4.24 (dq, J = 10.7,
7.1 Hz, 1 H), 3.39 (br s, 1 H), 3.27 (hept, J = 7.0
Hz, 1 H), 1.29 (t, J = 7.1
Hz, 3 H), 1.24 (t, J = 7.0
Hz, 3 H), 1.23 (t, J = 7.0 Hz,
3 H) ppm. ¹³C NMR (75 MHz, CDCl3,
293 K): δ = 173.4, 143.0, 141.8,
135.5, 119.9, 118.8, 118.0, 72.7, 62.9, 27.3, 22.5, 22.4, 14.1 ppm.
MS (ESI+): m/z = 277.1 [M + Na]+.
HRMS (ESI+): m/z [M + Na]+ calcd
for C13H18O5: 277.1052; found:
277.1034.
Compound 3g: IR (neat):
3482, 2939, 2839, 1731, 1612, 1589, 1507, 1207, 1157, 1065, 1030
cm-¹. ¹H NMR (500 MHz,
CDCl3, 293 K): δ = 7.15
(d, J = 8.5
Hz, 1 H), 6.45 (m, 2 H), 5.19 (d, J = 5.8
Hz, 1 H), 4.19 (dq, J = 10.8,
7.1 Hz,
1 H), 4.18 (dq, J = 10.8,
7.1 Hz, 1 H), 3.78 (s, 3 H), 3.77 (s, 3 H), 3.53 (d, J = 5.8 Hz,
1 H), 1.19 (t, J = 7.1
Hz, 3 H) ppm. ¹³C NMR (75 MHz, CDCl3,
293 K): δ = 174.0, 161.2, 158.3, 130.2,
119.9, 104.4, 99.0, 69.8, 61.7, 55.5, 55.4, 14.1 ppm. MS (ESI+): m/z = 263.1 [M + Na]+.
HRMS (ESI+): m/z [M + Na]+ calcd
for C12H16O5: 263.0895; found:
263.0893.
Compound 3h: IR (neat):
3442, 2891, 1727, 1614, 1523, 1354, 1180, 1074, 1012, 800 cm-¹. ¹H
NMR (500 MHz, CDCl3, 293 K): δ = 7.25
(d, J = 8.7
Hz, 2 H), 6.70 (d, J = 8.7 Hz,
2 H), 5.06 (s, 1 H), 4.26 (dq, J = 10.9,
7.0 Hz, 1 H), 4.16 (dq, J = 10.9,
7.0 Hz, 1 H), 3.27 (br s, 1 H), 2.95 (s, 6 H), 1.23 (t, J = 7.0 Hz,
3 H) ppm. ¹³C NMR (75 MHz, CDCl3, 293
K): δ = 174.3, 150.8, 127.7
(2 C), 126.3, 112.5 (2 C), 72.9, 62.0, 40.6 (2 C), 14.2 ppm. MS
(ESI+): m/z = 246.1
[M + Na]+,
224.1 [M + H]+, 206.1 [M - H2O + H]+.
HRMS (ESI+): m/z [M + H]+ calcd
for C12H17NO3: 224.1287; found: 224.1270.
Compound 3i: IR (neat): 3399, 2981, 1724, 1548,
1457, 1423, 1198, 1077, 1037, 743 cm-¹. ¹H
NMR (500 MHz, CDCl3, 293 K): δ = 8.40
(br s, 1 H), 7.71 (d, J = 7.9
Hz, 1 H), 7.29 (d, J = 8.2
Hz, 1 H), 7.20 (ddd, J = 8.2,
7.0, 1.0 Hz, 1 H), 7.14 (ddd, J = 8.2,
7.0, 0.9 Hz, 1 H), 7.08 (d, J = 2.3
Hz, 1 H), 5.46 (d, J = 5.5
Hz, 1 H), 4.28 (dq, J = 10.8,
7.0 Hz, 1 H), 4.16 (dq, J = 10.8,
7.0 Hz, 1 H), 3.51 (m, 1 H), 1.20 (t, J = 7.0
Hz, 3 H) ppm. ¹³C NMR (75 MHz, CDCl3,
293 K): δ = 174.1, 136.5, 125.4,
123.5, 122.5, 120.1, 119.4, 113.6, 111.6, 67.4, 62.1, 14.1 ppm.
MS (ESI+): m/z = 242.1 [M + Na]+,
202.1 [M - H2O + H]+.
HRMS (ESI+): m/z [M + Na]+ calcd
for C12H13NO3: 242.0793; found:
242.0805.
Compound 3j: IR (neat):
3369, 2981, 1730, 1492, 1368, 1299, 1203, 1052, 1018, 714 cm-¹. ¹H
NMR (500 MHz, CDCl3, 293 K): δ = 6.61
(t, J = 2.1
Hz, 1 H), 6.05 (d, J = 2.1 Hz,
2 H), 5.20 (d, J = 7.0
Hz, 1 H), 4.31 (dq, J = 10.9,
7.0 Hz, 1 H), 4.27 (dq, J = 10.9,
7.0 Hz, 1 H), 3.66 (s, 3 H), 3.15 (d, J = 7.0
Hz, 1 H), 1.29 (t, J = 7.0
Hz, 3 H) ppm. ¹³C NMR (75 MHz, CDCl3,
293 K): δ = 172.9, 129.2, 124.1,
108.5, 107.0, 66.4, 62.1, 34.1, 14.2 ppm. MS (ESI+): m/z = 206.1 [M + Na]+,
166.1 [M - H2O + H]+.
HRMS (ESI+): m/z [M + Na]+ calcd
for C9H13NO3: 206.0793; found:
206.0791.
We thank one of the referees for bringing up this important point.