Gold(I)-Catalysed Dehydrative Formation of Ethers From Benzylic Alcohols and Phenols

Transcription

1 Electronic Supplementary Material (ESI) for Green Chemistry. This journal is The Royal Society of Chemistry 205 Gold(I)-Catalysed Dehydrative ormation of Ethers rom Benzylic Alcohols and enols Richard M. P. Veenboer and Steven P. Nolan* EaStCEM, School of Chemistry University of St. Andrews, Purdie Building, North augh St. Andrews, ife, KT6 9ST (UK) Contents 2. GENERAL EXPERIMENTAL SECTIN INITIAL ALCL REACTIVITY SCREENING SLVENT SCREENING CARACTERISATIN DATA NMR SPECTRA REERENCES General experimental section Reactions were monitored using gas chromatography (GC) on a Agilent instrument: 90 C to 300 C at 45 C /min, µl injection volume, flow 6.5 µl/min, flame ionisation detector at 5 z, resolution of 0.04 min. Deuterated solvent (CD 3 ) was filtered through basic alumina in order to remove traces of. Nuclear Magnetic Resonance (NMR) spectra were recorded on Bruker Avance 300 Mz, 400 Mz and 500 Mz spectrometers. Chemical shifts are expressed in values (ppm) referenced internally to residual solvent resonances (, 7.26 ppm (CD 3 ); 3 C, 77.6 ppm (CD 3 )). Assignment was accomplished using 2D NMR techniques: - CSY, - 3 C SQC and - 3 C MBC. Peaks are assigned as s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet) or br (broad). Peaks of aromatic nuclei are assigned i (ipso), o (ortho), m (meta) or p (para), and benzyl or phenol (in subscript), referring to their origin in the starting alcohols. igh resolution mass spectrometry (RMS) was performed by the EPSRC National Mass Spectrometry Service Centre (NMSSC), Swansea University, Singleton Park, Swansea, SA2 8PP, UK. S

2 3. Initial alcohol reactivity screening The reactivity of various combinations of alcohols in the presence of [Au(IPr )(C 3 CN)][B 4 ] (c, 0.6 mol%, igure ) at 80 C under neat conditions was evaluated (Table S). In contrast to other reports using gold(i), or gold(iii) 2 catalysts, no ethers were formed from n-bu, i-pr or Bn (or mixtures of those alcohols) using the gold(i) catalyst c (Table S, entry ). The formation of symmetrical ethers from secondary benzylic alcohols is not only known to proceed in the presence of gold(i) complexes, 3 but also as by-products in reactions with arenes, 4 malonates, 5 or styrene 6 in the presence of other Lewis-acidic catalysts. Indeed, the formation of symmetrical ether 4a from 2a was observed under our test conditions (Table S, entries 2-3). We were delighted to observe the formation of unsymmetrical ether 5aa from the reaction of a secondary benzylic alcohol (2a) with a phenol (3a) (Table S, entry 4). 7 inally, no reaction occurred in the reaction of only phenol 3a (Table S, entry 5). Table S Evaluation of reactivity of combinations of alcohols. a Entry R + R 2 c (0.6 mol%) neat, 80 C R R 2 b R R n.r. 2 b R 2a 4a 3 2a 2a 4a 4 2a 3a 5aa 5 3a 3a n.r. a Reaction condition: R - (0.25 mmol), R - (0.25 mmol), neat, in air. b R = n-bu, i-pr, Bn. N.r. = no reaction. 4. Solvent screening Compared to the reaction between -phenylethanol (2a) and 4-fluorophenol (3a) under neat conditions (Table, entry 4), the use of C 3 CN as the reaction solvent shifted the product distribution towards symmetrical ether 4a (Table S2, entry ). In contrast to the report by ashmi and co-workers, the formation of amides was not observed under these conditions. 3a No reaction took place in dioxane (Table S2, entry 2). The reactions in DCE or toluene were much slower compared to the reaction under neat conditions, whilst the product distributions were only affected moderately (Table S2, entries 3-4), obtaining better conversion towards the desired product when toluene was used as solvent. This outcome suggested that toluene could be used to modulate the selectivity of the transformation. Table S2 Solvent screening. a 2a + 3a c (0.6 mol%) solvent 80 C 4a + Conversion (%) Entry Solvent t (h) (4a/5aa) b C 3 CN 0.25 >95 (67/33) 2 dioxane 3 0 3,2-DCE 3 6 (45/55) 4 C (3/69) a Reaction conditions: 2a (0.25 mmol), 3a (0.25 mmol), solvent (2.5 M), in air. b Determined by GC analysis, with respect to 2a. 5aa S2

3 5. Characterisation data -fluoro-4-(-phenylethoxy)benzene (5aa) According to the general procedure, a crude product, which was prepared from -phenylethanol (2a) (30.5 mg, 0.25 mmol), 4-fluorophenol (3a) (40. mg,.25 mmol) and [Au(IPr )(MeCN)][B 4 ] (c) (2.0 mg, 2.5 μmol,.0 mol%) at 50 C for 5 h, was purified by column chromatography on silica gel (petroleum ether/diethyl ether = 9/) to give 5aa (44.2 mg, 82%) as a colourless liquid. -NMR (500 Mz, CD 3 ): (m, 4; benzyl ), (m, 2; benzyl ), (m, 2; m- phenol ), (m, 2; o- phenol ), 5.22 (q, 3 J = 6.5 z, ; C),.62 (d, 3 J = 6.5 z, ; C 3 ). 3 C{ }-NMR (26 Mz, CD 3 ): 58.2 (C; i- phenol C), 57.3 (d, J C = z, C; p- phenol C), 43. (C; i- benzyl C), 28.8 (2C; benzyl C), 27.7 (C; p- benzyl C), 25.7 (2C; benzyl C), 7.2 (d, 3 J C = 8.0 z, 2C; o- phenol C), 5.8 (d, 2 J C = 22.9 z, 2C; m- phenol C), 76.9 (C; C), 24.6 (C; C3). 9 -NMR (282 Mz, CD 3 ): RMS (APCI) calcd for C 4 7 N [(M+N 4 ) + ] , found ((4-fluorophenoxy)methylene)dibenzene (5ab) According to the general procedure, a crude product, which was prepared from benzhydrol (2b) (46. mg, 0.25 mmol), 4-fluorophenol (3a) (40. mg,.25 mmol) and [Au(IPr )(MeCN)][B 4 ] (c) (2.0 mg, 2.5 μmol,.0 mol%) at 50 C for 5 h, was purified by column chromatography on silica gel (petroleum ether/diethyl ether = 9/) to give 5ab (59.8 mg, %) as a pale yellow liquid. -NMR (500 Mz, CD 3 ): (m, 4; benzyl ), (m, 4; benzyl ), (m, 2; p- phenol ), (m, 2; phenol ), 6.3 (s, ; C). 3 C{ }-NMR (26 Mz, CD 3 ): 57.5 (d, J C = z, C; p- phenol C), 54.3 (C; i- phenol C), 4.2 (2C; i- benzyl C), 28.8 (4C; m- benzyl C), 28.0 (2C; p- benzyl C), 27.0 (4C; o- benzyl C), 7.4 (d, 3 J C = 7.9 z, 2C; o- phenol C), 5.9 (d, 4 J C = 23.0 z, 2C; m- phenol C), 82.7 (C; C). 9 -NMR (470 Mz, CD3): RMS (ASAP) calcd for C 9 5 [(M) + ] 278.0, found fluoro-4-(-phenylpropoxy)benzene (5ac) According to the general procedure, a crude product, which was prepared from -phenyl--propanol (2c) (34.0 mg, 0.25 mmol), 4-fluorophenol (3a) (40. mg,.25 mmol) and [Au(IPr )(MeCN)][B 4 ] (c) (2.0 mg, 2.5 μmol,.0 mol%) at 50 C for 5 h, was purified by column chromatography on silica gel (petroleum ether/diethyl ether = 9/) to give 5ac (94.4 mg, 7%) as a colourless liquid. -NMR (500 Mz, CD 3 ): (m, 4; benzyl ), (m, 4; p- benzyl ), (m, 2; m- phenol ), (m, 2; m- phenol ), 4.93 (t, 3 J = 6.4 z, ; C), (m, ; C), (m, ; C),.00 (t, 3 J = 7.4 z, 3; C 3 ). 3 C{ }-NMR (26 Mz, CD 3 ): (d, J C = z, C; p- phenol C), 54.6 (C; i- phenol C), 4.8 (C; i- benzyl C), 28.6 (2C; m- benzyl C), 27.7 (C; p- benzyl C), 26.2 (2C; o- benzyl C), 7. (d, 3 J C = 7.8 z, 2C; o- phenol C), 5.7 (d, 2 J C = 22.9 z, 2C; m- phenol C), 82.5 (C; C), 3.7 (2C; C 2 ), 0.3 (C; C3). 9 -NMR (470 Mz, CD 3 ): RMS (EI) calcd for C 5 5 [(M) + ] , found S3

4 -fluoro-4-(2-methyl--phenylpropoxy)benzene (5ad) According to the general procedure, a crude product, which was prepared from 2-methyl--phenyl-- propanol (2d) (37.6 mg, 0.25 mmol), 4-fluorophenol (3a) (40. mg,.25 mmol) and [Au(IPr )(MeCN)][B 4 ] (c) (2.0 mg, 2.5 μmol,.0 mol%) at 50 C for 5 h, was purified by column chromatography on silica gel (petroleum ether/diethyl ether = 9/) to give 5ad (48.0 mg, 79%) as a colourless liquid. -NMR (500 Mz, CD 3 ): (m, 4; benzyl ), (m, 4; p- benzyl ), (m, 2; m- phenol ), (m, 2; m- phenol ), 4.70 (d, 3 J = 6.3 z, ; C), (m, ; C),.05 (d, 3 J = 6.6 z, 3; C 3 ), 0.90 (d, 3 J = 6.8 z, 3; C 3 ). 3 C{ }-NMR (26 Mz, CD 3 ): 57.2 (d, J C = z, C; p- phenol C), 54.9 (C; i- phenol C), 40.5 (C; i- benzyl C), 28.4 (2C; o- benzyl C), 27.6 (C; p- benzyl C), 27.0 (2C; m- benzyl C), 7. (d, 3 J C = 7.9 z, 2C; o- phenol C), 5.7 (d, 2 J C = 23.0 z, 2C; m- phenol C), 86.3 (C; C), 35.4 (C; C), 9. (C; C 3 ), 8.4 (C; C 3 ). 9 -NMR (470 Mz, CD 3 ): RMS (EI) calcd for C 6 7 [(M)+] , found (-(4-fluorophenoxy)ethyl)-2-methylbenzene (5ae) According to the general procedure, a crude product, which was prepared from -(2- methylphenyl)ethanol (2e) (34.0 mg, 0.25 mmol), 4-fluorophenol (3a) (40. mg,.25 mmol) and [Au(IPr )(MeCN)][B 4 ] (c) (2.0 mg, 2.5 μmol,.0 mol%) at 80 C for h, was purified by column chromatography on silica gel (petroleum ether/diethyl ether = 9/) to give 5ae (50.8 mg, 88%) as a colourless liquid. -NMR (500 Mz, CD 3 ): (m, ; benzyl ), (m, 4; benzyl ), (m, 2; m- phenol ), (m, 2; o- phenol ), 5.39 (q, 3 J = 6.4 z, ; C), 2.40 (s, 3; C 3 ),.59 (d, 3 J = 6.4 z, ; C 3 ). 3 C{ }-NMR (26 Mz, CD 3 ): 57.9 (d, J C = z, C; p- phenol C), 54. (C; i- phenol C), 4.0 (C; i- benzyl C), 33.9 (C; o- benzyl C), 30.7 (C; benzyl C), 27.4 (C; benzyl C), 26.9 (C; benzyl C), 25.2 (C; benzyl C), 6.74 (d, 3 J C = 8.0 z, 2C; o- phenol C), 5.8 (d, 2 J C = 23. z, 2C; m- phenol C), 73.7 (C; C), 22.9 (C; C 3 ), 9. (C; C 3 ). 9 -NMR (376 Mz, CD 3 ): RMS (APCI) calcd for C 5 9 N [(M+N 4 ) + ] , found chloro-4-(-(4-fluorophenoxy)ethyl)benzene (5ah) According to the general procedure, a crude product, which was prepared from -(4- chlorophenyl)ethanol (2h) ( 39.2 mg, 0.25 mmol), 4-fluorophenol (3a) (40. mg,.25 mmol) and [Au(IPr )(MeCN)][B 4 ] (c) (2.0 mg, 2.5 μmol,.0 mol%) at 50 C for 5 h, was purified by column chromatography on silica gel (petroleum ether/diethyl ether = 9/) to give 5ah (36.2 mg, 58%) as a pale yellow liquid. -NMR (500 Mz, CD 3 ): (m, 4; benzyl ), (m, 2; phenol ), (m, 2; phenol ), 5.9 (q, 3 J = 6.4 z, ; C),.60 (d, 3 J = 6.5 z, 3; C 3 ). 3 C{ }-NMR (26 Mz, CD 3 ): 57.4 (d, J C = z, C; p- phenol C), 53.9 (C; i- phenol C), 4.6 (C; o- benzyl C), 33.4 (C; p- benzyl C), 29.0 (2C; m- benzyl C), 27. (2C; o- benzyl C), 7.2 (d, 3 J C = 8.0 z, 2C; o- phenol C), 5.9 (d, 2 J C = 22.9 z, 2C; m- phenol C), 76.3 (C; C), 24.5 (C; C 3 ). 9 -NMR (47 Mz, CD 3 ): RMS (EI) calcd for C 4 2 [(M) + ] , found S4

5 -fluoro-4-(-(4-fluorophenoxy)ethyl)benzene (5ai) According to the general procedure, a crude product, which was prepared from -(4- fluorophenyl)ethanol (2i) (35.0 mg, 0.25 mmol), 4-fluorophenol (3a) (40. mg,.25 mmol) and [Au(IPr )(MeCN)][B 4 ] (c) (2.0 mg, 2.5 μmol,.0 mol%) at 50 C for 5 h, was purified by column chromatography on silica gel (petroleum ether/diethyl ether = 9/) to give 5ai (45.9 mg, 78%) as a pale yellow liquid. -NMR (500 Mz, CD 3 ): (m, 2; benzyl ), (m, 2; benzyl ), (m, 2; phenol ), (m, 2; phenol ), 5.20 (q, 3 J = 6.4 z, ; C),.60 (d, 3 J = 6.5 z, 3; C 3 ). 3 C{ }-NMR (26 Mz, CD 3 ): (d, J C = z, C; p- benzyl C), 57.4 (d, J C = z, C; p- phenol C), 54.0 (C; i- phenol C), 38.8 (C; i- benzyl C), 27.4 (d, 3 J C = 8. z, 2C; o- phenol C), 7.3 (d, 3 J C = 8.0 z, 2C; m- benzyl C), 5.9 (d, 2 J C = 23. z, 2C; m- phenol C), 5.7 (d, 2 J C = 2.4 z, 2C; m- benzyl C), 76.3 (C; C), 24.6 (C; C 3 ). 9 -NMR (47 Mz, CD 3 ): -4.9, RMS (EI) calcd for C 6 7 [(M) + ] , found chloro-4-(-phenylethoxy)benzene (5ba) According to the general procedure, a crude product, which was prepared from -phenylethanol (2a) (30.5 mg, 0.25 mmol), 4-chlorophenol (3b) (60.7 mg,.25 mmol) and [Au(IPr )(MeCN)][B 4 ] (c) (2.0 mg, 2.5 μmol,.0 mol%) in 50 μl toluene at 50 C for 5 h, was purified by column chromatography on silica gel (petroleum ether/diethyl ether = 9/) to give 5ba (33.7 mg, 58%) as a pale yellow solid. -NMR (500 Mz, CD 3 ): (m, 4; benzyl ), (m, ; benzyl ), 7.3 (dt, 3 J = 9.9 z, 5 J = 2.9 z, 2; phenol ), 6.77 (dt, 3 J = 9.9 z, 5 J = 2.9 z, 2; phenol ), 5.25 (q, 3 J = 6.5 z, ; C),.63 (d, 3 J = 6.5 z, 3; C 3 ). 3 C{ }-NMR (26 Mz, CD 3 ): 56.7 (C; i- phenol C), 42.9 (C; i- benzyl C), 29.3 (2C; m- phenol C), 28.8 (2C; benzyl C), 27.7 (C; p- benzyl C), 25.6 (3C; benzyl C + p- phenol C), 7.3 (2C; o- phenol C), 76.5 (C; C), 24.6 (C; C 3 ). RMS (EI) calcd for C 4 3 [(M) + ] , found ((4-chlorophenoxy)methylene)dibenzene (5bb) According to the general procedure, a crude product, which was prepared from benzhydrol (2b) (46. mg, 0.25 mmol), 4-chlorophenol (3b) (60.7 mg,.25 mmol) and [Au(IPr )(MeCN)][B 4 ] (c) (2.0 mg, 2.5 μmol,.0 mol%) in 00 μl at 50 C for 5 h, was purified by column chromatography on silica gel (petroleum ether/diethyl ether = 9/) to give 5bb (59.0 mg, 80%) as a pale yellow solid. -NMR (500 Mz, CD 3 ): (m, 4; o- benzyl ), (m, 4; m- benzyl ), (m, 2; p- benzyl ), 7.6 (dd, 3 J = 9.8 z, 5 J = 2.8 z, 2; m- phenol ), 6.87 (dd, 3 J = 9.8 z, 5 J = 2.8 z, 2; o- phenol ), 6.6 (s, ; C). 3 C{ }-NMR (26 Mz, CD 3 ): 56.8 (C; i- phenol C), 40.9 (2C; i- benzyl C), 29.4 (2C; m- phenol C), 28.8 (4C; m- benzyl C), 28.0 (2C; p- benzyl C), 27.0 (4C; o- benzyl C), 26.0 (C; p- phenol C), 7.6 (2C; o- phenol C), 82.2 (C; C). RMS (EI) calcd for C 9 5 [(M) + ] , found chloro-4-(-phenylpropoxy)benzene (5bc) According to the general procedure, a crude product, which was prepared from -phenyl--propanol (2c) (34.0 mg, 0.25 mmol), 4-chlorophenol (3b) (60.7 mg,.25 mmol) and [Au(IPr )(MeCN)][B 4 ] (c) (2.0 mg, 2.5 μmol,.0 mol%) at 50 C for 5 h, was purified by column chromatography on silica gel (petroleum ether/diethyl ether = 9/) to give 5bc (36.4 mg, 59%) as a colourless liquid. -NMR (500 Mz, CD 3 ): (m, 4; benzyl ), (m, ; p- benzyl ), (m, 2; m- phenol ), (m, 2; o- phenol ), (m, ; C), (m, ; C 2 ), (m, ; C 2 ),.00 (t, 3 J = 7.4 z, 3; C 3 ). 3 C{ }-NMR (26 Mz, CD 3 ): 57. (C; i- phenol C), 4.6 (C; i- benzyl C), 29.3 (2C; m- phenol C), 28.7 (2C; benzyl C), 27.7 (2C; p- benzyl C), 26.2 (2C; benzyl C), 25.5 (C; p- phenol C), 7.3 (2C; o- phenol C), 82.0 (C; C), 3.7 (C; C 2 ), 0.3 (C; C 3 ). RMS (EI) calcd for C 5 5 [(M) + ] , found S5

6 -chloro-4-(2-methyl--phenylpropoxy)benzene (5bd) According to the general procedure, a crude product, which was prepared from 2-methyl--phenyl-- propanol (2d) (37.6 mg, 0.25 mmol), 4-chlorophenol (3b) (60.7 mg,.25 mmol) and [Au(IPr )(MeCN)][B 4 ] (c) (2.0 mg, 2.5 μmol,.0 mol%) at 50 C for 5 h, was purified by column chromatography on silica gel (petroleum ether/diethyl ether = 9/) to give 5bd (58.4 mg, 93%) as a colourless liquid. -NMR (500 Mz, CD 3 ): (m, 5; benzyl ), 7.0 (dt, 3 J = 9.8 z, 4 J = 2.8 z, 2; m- phenol ), 6.75 (dt, 3 J = 9.8 z, 4 J = 2.8 z, 2; o- phenol ), 4.74 (d, J = 6.3 z, ; C), (m, ; C),.05 (d, 3 J = 6.7 z, 3; C 3 ), 0.90 (d, 3 J = 6.8 z, 3; C 3 ). 3 C{ }-NMR (26 Mz, CD 3 ): 57.3 (C; i-c phenol C), 40.2 (C; i- benzyl C), 29.2 (2C; m- phenol C), 28.4 (2C; benzyl C), 27.7 (C; p- benzyl C), 26.9 (2C; benzyl C), 25.4 (C; p- phenol C), 7.3 (2C; o- phenol C), 85.8 (C; C), 35.3 (C; C), 9. (C; C 3 ), 8.3 (C; C 3 ). RMS (EI) calcd for C 6 7 [(M) + ] , found (-(4-chlorophenoxy)ethyl)-2-methylbenzene (5be) According to the general procedure, a crude product, which was prepared from -(2- methylphenyl)ethanol (2e) (34.0 mg, 0.25 mmol), 4-chlorophenol (3b) (60.7 mg,.25 mmol) and [Au(IPr )(MeCN)][B 4 ] (c) (2.0 mg, 2.5 μmol,.0 mol%) at 50 C for 5 h, was purified by column chromatography on silica gel (petroleum ether/diethyl ether = 9/) to give 5be (55. mg, 89%) as a colourless liquid. -NMR (500 Mz, CD 3 ): (m, ; benzyl ), (m, 3; benzyl ), (m, 2; m- phenol ), (m, 2; o- phenol ), 5.4 (q, 3 J = 6.4 z, ; C), 2.4 (s, 3; C 3 ),.6 (d, 3 J = 6.4 z, 3; C 3 ). 3 C{ }-NMR (26 Mz, CD 3 ): 56.6 (C; i- phenol C), 40.8 (C; i- benzyl C), 33.9 (C; o- benzyl C), 30.7 (2C; m- phenol C), 29.3 (2C; benzyl C), 27.5 (C; benzyl C), 26.8 (C; benzyl C), 25.5 (C; p- phenol C), 25. (C; benzyl C), 7.0 (2C; o- phenol C), 73.4 (C; C), 22.9 (C; C 3 ), 9. (C; C 3 ). RMS (EI) calcd for C 5 5 [(M) + ] , found chloro-4-(-(4-chlorophenoxy)ethyl)benzene (5bf) According to the general procedure, a crude product, which was prepared from -(2-chlorophenyl)ethanol (2f) (39.2 mg, 0.25 mmol), 4-chlorophenol (3b) (60.7 mg,.25 mmol) and [Au(IPr )(MeCN)][B 4 ] (c) (2.0 mg, 2.5 μmol,.0 mol%) at 80 C for h, was purified by column chromatography on silica gel (petroleum ether/diethyl ether = 9/) to give 5bf (42.9 mg, 64%) as a yellow liquid. -NMR (500 Mz, CD3): 7.43 (dd, 3 J = 7.3 z, 4 J = 2. z, ; benzyl ), 7.36 (dd, 3 J = 7.2 z, 4 J = 2.0 z, ; benzyl ), (m, 2; benzyl ), 7.4 (dt, 3 J = 9.8 z, 2 J = 2.8 z, 2; m- phenol ), 6.72 (dt, 3 J = 9.8 z, 2 J = 2.8 z, 2; o- phenol ), 5.64 (q, 3 J = 6.4 z, ; C),.62 (d, 3 J = 6.3 z, 3; C 3 ). 3 C{ }-NMR (26 Mz, CD 3 ): 56.4 (C; i- phenol C), 4.4 (C; i- benzyl C), 33.4 (C; p- benzyl C), 29.4 (2C; m- phenol C), 29.0 (2C; m- benzyl C), 27. (2C; o- benzyl C), 7.3 (2C; o- phenol C), 75.9 (C; C), 24.5 (C; C 3 ). RMS (EI) calcd for C [(M) + ] , found chloro-2-(-(4-chlorophenoxy)ethyl)benzene (5bh) According to the general procedure, a crude product, which was prepared from -(4- chlorophenyl)ethanol (2h) ( 39.2 mg, 0.25 mmol), 4-chlorophenol (3b) (60.7 mg,.25 mmol) and [Au(IPr )(MeCN)][B 4 ] (c) (2.0 mg, 2.5 μmol,.0 mol%) at 50 C for 5 h, was purified by column chromatography on silica gel (petroleum ether/diethyl ether = 9/) to give 5bh (48.9 mg, 73%) as a colourless liquid. -NMR (500 Mz, CD 3 ): (m, 4; benzyl ), 7.4 (dt, 3 J = 9.8 z, 4 J = 2.8 z, 2; m- phenol ), 6.75 (dt, 3 J = 9.8 z, 4 J = 2.8 z, 2; o- phenol ), 5.23 (q, 3 J = 6.4 z, ; C),.60 (d, 3 J = 6.4 z, 3; C 3 ). 3 C{ }-NMR (26 Mz, CD 3 ): 56.2 (C; i- phenol C), 40.2 (C; i- benzyl C), 3.7 (C; o- benzyl C), 29.6 (C; benzyl C), 29.4 (2C; m- benzyl C), 28.9 (C; benzyl C), 27.7 (C; benzyl C), 26.8 (C; benzyl C), 25.7 (C; p- phenol C), 6.9 (2C; o- benzyl C), 72.7 (C; C), 22.7 (C; C 3 ).RMS (EI) calcd for C [(M) + ] , found S6

7 -chloro-4-(-(4-fluorophenyl)ethoxy)benzene (5bi) According to the general procedure, a crude product, which was prepared from -(4- fluorophenyl)ethanol (2i) (35.0 mg, 0.25 mmol), 4-chlorophenol (3b) (60.7 mg,.25 mmol) and [Au(IPr )(MeCN)][B 4 ] (c) (2.0 mg, 2.5 μmol,.0 mol%) in 50 μl toluene at 80 C for h, was purified by column chromatography on silica gel (petroleum ether/diethyl ether = 9/) to give 5bi (5.5 mg, 82%) as a colourless liquid. -NMR (500 Mz, CD 3 ): (m, 2; m- benzyl ), 7.4 (dt, 3 J = 9.8 z, 4 J = 2.8 z, 2; m- phenol ), (m, 2; o- benzyl ), 6.76 (dt, 3 J = 9.8 z, 4 J = 2.8 z, 2; o- phenol ), 5.24 (q, 3 J = 6.4 z, ; C),.6 (d, 3 J = 6.4 z, 3; C 3 ). 3 C{ }-NMR (26 Mz, CD 3 ): 57.5 (d, J C = z, p- benzyl C), 56.4 (C; i- phenol C), 38.6 (C; i- benzyl C), 29.4 (2C; m- phenol C), 27.3 (d, 3 J C = 8. z, o- benzyl C), 7.4 (2C; o- phenol C), 5.74 (d, 2 J = 2.5 z, 2C; m- benzyl C), 75.9 (C; C), 24.6 (C; C 3 ). 9 -NMR (470 Mz, CD 3 ): RMS (EI) calcd for C 4 2 [(M) + ] , found S7

8 6. NMR Spectra -fluoro-4-(-phenylethoxy)benzene (5aa) 3 C{ } S8

9 ((4-fluorophenoxy)methylene)dibenzene (5ab) 3 C{ } S9

10 -fluoro-4-(-phenylpropoxy)benzene (5ac) 3 C{ } S0

11 -fluoro-4-(2-methyl--phenylpropoxy)benzene (5ad) 3 C{ } S

12 -(-(4-fluorophenoxy)ethyl)-2-methylbenzene (5ae) 3 C{ } S2

13 -chloro-4-(-(4-fluorophenoxy)ethyl)benzene (5ah) 3 C{ } S3

14 -fluoro-4-(-(4-fluorophenoxy)ethyl)benzene (5ai) 3 C{ } S4

15 -chloro-4-(-phenylethoxy)benzene (5ba) 3 C{ } S5

16 ((4-chlorophenoxy)methylene)dibenzene (5bb) 3 C{ } S6

17 -chloro-4-(-phenylpropoxy)benzene (5bc) 3 C{ } S7

18 -chloro-4-(2-methyl--phenylpropoxy)benzene (5bd) 3 C{ } S8

19 -(-(4-chlorophenoxy)ethyl)-2-methylbenzene (5be) 3 C{ } S9

20 -chloro-4-(-(4-chlorophenoxy)ethyl)benzene (5bf) 3 C{ } S20

21 -chloro-2-(-(4-chlorophenoxy)ethyl)benzene (5bh) 3 C{ } S2

22 -chloro-4-(-(4-fluorophenyl)ethoxy)benzene (5bi) 3 C{ } S22

23 7. References. Liu, Y.; Wang, X.; Wang, Y.; Du, C.; Shi,.; Jin, S.; Jiang, C.; Xiao, J.; Cheng, M., Adv. Synth. Catal. 205, doi: 0.002/adsc Cuenca, A. B.; Mancha, G.; Asensio, G.; Medio-Simón, M., Chem. Eur. J. 2008, 4, (a) Ibrahim, N.; ashmi, A. S. K.; Rominger,., Adv. Synth. Catal. 20, 353, ; (b) Veenboer, R. M. P.; Dupuy, S.; Nolan, S. P., ACS Catalysis 205, 5, (a) Podder, S.; Choudhury, J.; Roy, S., J. rg. Chem. 2007, 72, ; (b) Le Bras, J.; Muzart, J., Tetrahedron 2007, 63, Yasuda, M.; Somyo, T.; Baba, A., Angew. Chem. Int. Ed. 2006, 45, Wagh, K. V.; Bhanage, B. M., RSC Advances 204, 4, enol 3a was chosen because its fluorine substituent presents a diagnostic aid for NMR analysis. S23