Supporting Information

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1 Supporting Information Doubly Regioselective C H Hydroarylation of Unsymmetrical Alkynes Using Carboxylates as Deciduous Directing Groups Agostino Biafora, Bilal A. Khan,* Janet Bahri, Joachim M. Hewer, and Lukas J. Goossen* Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, Universitätsstr. 150, Bochum, (Germany). Department of Chemistry, University of Azad Jammu and Kashmir, Muzaffarabad, AJK, Pakistan FB Chemie und Forschungszentrum PTIMAS, Technische Universität Kaiserslautern, Erwin- Schrodinger-Str. Geb. 5-54, Kaiserslautern (Germany). lukas.goossen@rub.de bkhan@ajku.edu.pk. List of Contents General methods... Screening of the reaction conditions... Control experiments... 5 Control experiment for the deciduous character of the CH group:... 5 Reaction at longer reaction time:... 6 Mechanistic experiments:... 6 In-situ ESI-MS experiments:... 6 General procedures... 8 Synthesis and characterization of the corresponding products... 9 Synthesis of [Ru(4-Me-benzoato - -C 6, 1 )(hexamethylbenzene)(pyridine)] (6a)... 3 References NMR spectra S1

2 General methods Chemicals and solvents were either purchased (puriss p.a.) from commercial suppliers or purified by standard procedures prior to use. Reactions were performed in oven-dried glassware under a nitrogen atmosphere containing a Teflon-coated stirring bar and dry septum. Solvents were degassed with Argon prior to use. All reactions were monitored by GC using n-tetradecane as an internal standard. Response factors of the products with regard to n-tetradecane were obtained experimentally by analyzing known quantities of the substances. GC analyzes were carried out using an HP-5 capillary column (Phenyl methyl siloxane, 30 m , 100/ /3, min at 60 C, heating rate 30 C min -1, 3 min at 300 C). Column chromatography was performed using a Combi Flash Companion-Chromatography-System (Isco-Systems) and Reveleris packed columns (40 g). NMR spectra were recorded on Bruker Avance 400 at ambient temperature using CDCl 3 as solvent, with proton and carbon resonances at 400 and 101 MHz respectively. Mass spectral data were acquired on a Varian GC-MS Saturn 100 T. CHN-elemental analysis was performed with a Hanau Elemental Analyzer vario Micro cube. Melting points were measured on a Mettler FP 61 and infrared spectra on a Perkin Elmer Spectrum 100 ATR-FTIR. Screening of the reaction conditions Table S1: Screening experiments for the regioselective decarboxylative C-H hydroarylation of unsymmetrical alkynes with arenecarboxylic acids. [a] # cat. (mol%) solvent base (eq.) add. 1 (eq.) add. (eq.) S 1a:a (eq.) Yield (%) [b] 3aa 3aa 4aa 1 [(p-cym)rucl ] -picoline PhMe GuanC (4) 3 (0.) AcH (1) (0.) 1:1 5 n.d. 1 [(p-cym)rui ] (4) `` `` `` `` `` 9 `` 19 3 [(C 6 Me 6 )RuCl ] (4) `` `` `` `` `` 16 `` 3 4 [(C 6 Me 3 )RuCl ] (4) `` `` `` `` `` 13 `` 9 5 [(C 6 H 6 )RuCl ] (4) `` `` `` `` `` 8 `` 3 6 [(p-cym)rucl ] (4) NMP `` `` `` `` trace 7

3 7 [(p-cym)rui ] (4) `` `` `` `` `` `` 3 8 [(C 6 Me 6 )RuCl ] (4) `` `` `` `` `` 38 `` 0 9 [C 6 Me 3 )RuCl ] (4) `` `` `` `` `` 15 `` [(C 6 H 6 )RuCl ] (4) `` `` `` `` `` 9 `` [(C 6 Me 6 )RuCl ] (4) C 6 Me 3 `` `` `` `` 15 `` 30 1 `` DMF `` `` `` `` n.d. `` n.d. 13 `` DMAc `` `` `` `` 1 `` 3 14 `` NCyP `` `` `` `` 18 `` 3 15 `` Propylene carbonate `` `` `` `` 18 `` trace 16 `` NMP `` `` `` 1: `` `` `` PivH (1) `` `` 4 `` `` `` `` AdCH (1) `` `` 44 `` `` `` `` TFA (1) `` `` n.d. n.d. n.d. 0 `` `` `` MesCH (1) `` `` 6 trace 7 1 `` `` `` AcH (1) - `` 64 `` 3 `` `` - `` - `` n.d. n.d. n.d. 3 `` `` GuanC 3 (0.) - - `` `` `` `` 4 `` `` Li C 3 (0.) AcH (1) - `` K C 3 (0.) - `` `` `` Cs C 3 (0.) `` - `` `` `` K C 3 (0.05) `` - `` `` `` K C 3 (0.1) `` - `` `` `` `` 9 `` `` K C 3 (0.3) `` - `` `` `` K C 3 (0.5) `` - `` `` `` K C 3 (1) `` - `` `` `` K C 3 (0.1) `` GuanC 3 (0.) `` `` `` `` `` GuanC 3 (0.05) `` `` `` `` MesC H (0.5) - `` `` `` `` MesC H (1) - `` `` `` `` MesC H GuanC 3 (0.5) (0.05) `` `` `` `` MesC H (1) `` `` 71 n.d. 38 `` `` DABC (1) `` `` `` 1 trace `` `` NEt 3 (1) `` `` `` 15 `` `` `` Quinuclidine (1) `` `` `` 11 `` 40 [a] Reaction conditions: 1a (0.5 mmol), a, [M], base, solvent, 10 C, 16 h under N - atmosphere. [b] Yields of corresponding methyl esters determined by GC after esterification with K C 3 ( eq.) and MeI (5 eq.) in NMP using n-tetradecane as the internal standard. Table S: Screening of organic bases. [a] S3

4 # base (1 eq.) Yield (%) [b] 3aa 3aa 4aa 1 triethylamine 13 n.d. 47 TMEDA 9 `` 14 3 diisopropylethylamin 15 `` 6 4 N-Me-tetramethylpiperidine 16 `` 38 5 Quinuclidine 11 `` 54 6 DBU 5 `` 10 7 N-Me-pyrrolidine 10 `` 10 8 TBAH 30H TBAAc [a] Reaction conditions: 1a (0.5 mmol), (0.75 mmol), [(p-cym)rucl ] (4 mol%), base, PhMe ( ml), 10 C, 16 h under N -atmosphere. [b] Yields of corresponding methyl esters determined by GC after esterification with K C 3 ( eq.) and MeI (5 eq.) in NMP using n-tetradecane as the internal standard. Table S3: Screening of microwave conditions for simple benzoic acid. [a] # t (min) µw T ( C) Yield (%) [b] 3za 3 za 5za trace `` `` `` trace `` S4

5 trace n.d. 180 [c] trace `` `` trace `` `` n.d trace `` `` `` `` trace `` `` `` 10 0 `` `` [a] Reaction conditions: 1a (0.5 mmol), (0.75 mmol), [(C 6 Me 6 )RuCl ] (4 mol%), K C 3 (10 mol%), NMP (1 ml), µw-irradiation, t, under N -atmosphere. [b] Yields of corresponding products determined by GC using n-tetradecane as the internal standard. [c] conventional heating after 16 h. Control experiments Control experiment for the deciduous character of the CH group: Scheme S1. Standard decarboxylative hydroarylation reaction set-up. S5

6 Scheme S. Decarboxylative reaction set-up reported by Hartwig and Zhao. Reaction at longer reaction time: Scheme S3. Standard reaction condition vs. prolonged reaction time. Mechanistic experiments: Scheme S4. Reaction from preformed ruthenacycle. In-situ ESI-MS experiments: General procedure for ESI-MS experiments: In-situ ESI-MS experiments were performed for three parallel reactions with standard reaction conditions: Measurement 1: reaction mixture was analyzed immediately after addition of all components (t=0, T=r.t.). Measurement : reactions mixture was analyzed immediately after the reactiontemperature was reached (t=0, T=10 C). Measurement 3: reaction mixture was analyzed after 3 h at 10 C (t=3h, T=10 C). S6

7 ESI-MS data were generated via electrospray ionization (ESI) from an MeCN solution with a concentration of approximately 0.1 mm and, if required, acidified with 5 µl of formic acid. The solutions were infused continously into the ESI chamber with a syringe pump at a flow rate of µl/min. We used nitrogen as nebulizer gas at a pressure of 7 to 8 psi and as a drying gas with a temperature of 00 C and a flow rate of 1 to L/min. The electrospray needle was held at 4.5 kv. The mass spectra were recorded using a Paul-type ion trap mass spectrometer (AmaZon ETD, Bruker Daltonics). The ion source was operated in the positive and negative electrospray ionization mode. The scan speed was 3500 m/z per second with a resolution of 0.3 FWHM, the scan range was at least from 50 to 1500 m/z. The Instrument was controlled by BrukerTrapControl 7. software, data analysis was done with BrukerDataAnalysis 4. software. Scheme S5. standard decarboxylative hydroarylation reaction set-up for ESI-MS experiments. Scheme S6. ESI-MS measurement of the reaction mixture (t = 0, room temperature). S7

8 Scheme S7. ESI-MS measurement of the reaction mixture (t = 0, 10 C). Scheme S8. ESI-MS measurement of the reaction mixture (t = 3h, 10 C). General procedures for the regioselective decarboxylative C-H hydroarylation of unsymmetrical alkynes with arenecarboxylic acids Method A: An oven-dried 0 ml vessel was charged with dichloro(hexamethylbenzene)ruthenium(ii) dimer (13.4 mg, 0.0 mmol, 4 mol%), guanidine carbonate (4.6 mg, 0.05 mmol, 5 mol%),,4,6-trimethylbenzoic acid (8.9 mg, 0.5 mmol, 1 eq.), potassium carbonate (6.98 mg, 0.05 mmol, 10 mol%) and the benzoic acid 1 (0.5 mmol). After flushing the vessel with 3 alternating vacuum and nitrogen purge cycles, degassed NMP (1 ml), and internal alkyne (0.75 mmol) was added via syringe. The resulting mixture was stirred at 10 C for 16 h. Lithium chloride (0%) was added and the resulting mixture was extracted with ethyl acetate (3 0 ml). The organic layers were washed with brine (0 ml). The combined organic layers were dried over MgS 4, filtered, and the volatiles were removed under reduced pressure. The residue was purified by column chromatography (Si, ethyl acetate/pentane or cyclohexane gradient) yielding the corresponding vinylarenes. S8

9 Method B: An oven-dried -ml microwave vial was charged with the dichloro(hexamethylbenzene)ruthenium(ii) dimer (13.4 mg, 0.0 mmol, 4 mol%), guanidine carbonate (9 mg, 0.05 mmol, 10 mol%),,4,6-trimethylbenzoic acid (41 mg, 0.5 mmol, 0.5 eq.), and the benzoic acid 1 (1 mmol). After flushing the vessel with 3 alternating vacuum and nitrogen purge cycles, degassed NMP ( ml), and internal alkyne (0.5 mmol) was added via syringe. The resulting mixture was first stirred in a water bath at 50 C for 10 min then irradiated in the microwave at 180 C for 5 min. at a maximum power of 50 W, then air-jet cooled. Lithium chloride (0%) was added and the resulting mixture was extracted with ethyl acetate (3 0 ml). The organic layers were washed with brine (0 ml). The combined organic layers were dried over MgS 4, filtered, and the volatiles were removed under reduced pressure. The residue was purified by column chromatography (Si, ethyl acetate/pentane or cyclohexane gradient) yielding the corresponding vinylarenes. Synthesis and characterization of the corresponding products 1-((E)--(3-methoxyphenyl)prop-1-enyl)benzene (3aa) CAS [ ] Compound 3aa was prepared following general procedure A, starting from 4-methoxybenzoic acid (1a) (90 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3aa was obtained as colorless liquid (80 mg, 0.34 mmol, 71%). Compound 3aa was prepared following general procedure B, starting from 4-methoxybenzoic acid (1a) (180 mg, 1 mmol) and 1-phenyl-1-propyne (a) (89 mg, 64 µl, 0.5 mmol). After purification, 3aa was obtained as colorless liquid (85 mg, 0.38 mmol, 76%). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 4 H) (m, H) (m, 1 H) (m, 1 H) (m, H) 3.83 (s, 3 H).5 (d, J=1.3 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), 138. (s), (s), 19. (s), 19.1 (s), 18. (s), 17.8 (s), 16.5 (s), (s), 11.4 (s), 11.0 (s), 77.3 (s), 76.7 (s), 55.3 (s), 17.5 (s) ppm. S9

10 IR: ṽ = 30, 996, 941, 834, 1597, 1576, 1485,147, 184, 119, 1170, 85, 775 cm -1. MS (EI, 70 ev) m/z (%): 5.0 (19), 4.0 (100) [M + ], 3. (13), 09. (63), 08.3 (15), 194. (4), 193. (14). HRMS (EI-TF) calcd. for C 16 H 16 : 4.101; found Methyl-3-((E)-1-phenylprop-1-en--yl)benzene (3ba) CAS [ ] Compound 3ba was prepared following general procedure A, starting from -methylbenzoic acid (1b) (69.5 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3ba was obtained as colorless liquid (75 mg, 0.36 mmol, 7%). Compound 3ba was prepared following general procedure B, starting from -methylbenzoic acid (1b) (140 mg, 1 mmol) and 1-phenyl-1-propyne (a) (59 mg, 64 µl, 0.5 mmol). After purification, 3ba was obtained as colorless liquid (73 mg, 0.35 mmol, 71%). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 6 H) (m, H) 7.13 (d, J=7.0 Hz, 1 H) 6.84 (d, J=1.3 Hz, 1 H).4 (s, 3 H).30 (d, J=1.3 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), (s), 19.1 (s), 18. (s), 18.1 (s), 17.9 (s), 17.5 (s), 16.8 (s), 16.4 (s), 13.1 (s), 77.3 (s), 76.7 (s), 1.6 (s), 17.5 (s) ppm. IR: ṽ = 303, 958, 97, 871, 1601, 1493, 1455,1377, 781, 698 cm -1. MS (EI, 70 ev) m/z (%): 09.1 (16), 08.1 (100) [M + ], 194. (13), (85), 178. (7), (1), 89. (1). HRMS (EI-TF) calcd. for C 16 H 16 : ; found Ethyl-3-((E)-1-phenylprop-1-en--yl)benzene (3ca) S10

11 Compound 3ca was prepared following general procedure, starting from -ethylbenzoic acid (1c) (75.1 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3ca was obtained as colorless liquid (89 mg, 0.4 mmol, 80 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 6 H) 7.1 (d, J=8.0 Hz, 1 H) 7.15 (s, 1 H) 7.05 (s, 1 H) 6.74 (d, J=1.3 Hz, 1 H).60 (d, J=7.5 Hz, H).19 (d, J=1.5 Hz, 3 H) 1.18 (t, J=7.5 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = 144. (s), (s), (s), (s), 19.1 (s), 18.3 (s), 18.1 (s), 17.5 (s), 16.8 (s), 16.4 (s), 15.6 (s), 13.4 (s), 77.3 (s), 76.7 (s), 9.0 (s), 17.6 (s), 15.7 (s) ppm. IR: ṽ = 303, 958, 97, 871, 1601, 1493, 1455,1377, 781, 698 cm -1. MS (EI, 70 ev) m/z (%): 3.0 (1),.1 (100) [M + ], 08. (9), 07. (44), 193. (14), 19. (10), (6). HRMS (EI-TF) calcd. for C 17 H 18 :.1400; found ((Z)-1-phenylprop-1-en--yl)-3-(E)-prop-1-enyl)benzene (3da) Compound 3da was prepared following general procedure, starting from -allylbenzoic acid (1d) (83 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3da was obtained as colorless liquid (75 mg, 0.3 mmol, 61 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = 7.48 (t, J=.0 Hz, 1 H) (m, 5 H) (m, 4 H) 6.84 (d, J=1.5 Hz, 1 H) (m, 1 H) 6.30 (dd, J=15.7, 6.7 Hz, 1 H).9 (d, J=1.5 Hz, 3 H) 1.9 (dd, J=6.5, 1.8 Hz, 3 H) ppm. S11

12 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), 137. (s), (s), 18.8 (s), 18.1 (s), 17.8 (s), 17.3 (s), 16.1 (s), 15.6 (s), 14.3 (s), 14. (s), 13.4 (s), 76.9 (s), 76.7 (s), 76.4 (s), 18. (s), 17. (s) ppm. IR: ṽ = 301, 913, 1700, 1597, 1576, 1491,1443, 1377, 961, 771 cm -1. MS (EI, 70 ev) m/z (%): 35. (19), 34. (100) [M + ], 0. (8), 19. (45), 04.3 (9), (10), 115. (13). HRMS (EI-TF) calcd. for C 18 H 18 : ; found Methoxy-3-((Z)-1-phenylprop-1-en--yl)benzene (3ea) CAS [ ] Compound 3ea was prepared following general procedure, starting from -methoxybenzoic acid (1e) (77 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3ea was obtained as colorless liquid (88 mg, 0.39 mmol, 79 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = 7.8 (d, J=.3 Hz, 4 H) (m, H) (m, 1 H) (m, 1 H) (m, H) 3.75 (s, 3 H).18 (d, J=1.3 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), 138. (s), (s), 19. (s), 19.1 (s), 18. (s), 17.8 (s), 16.5 (s), (s), 11.4 (s), 11.0 (s), 77.3 (s), 76.7 (s), 55.3 (s), 17.5 (s) ppm. IR: ṽ = 30, 996, 941, 834, 1597, 1576, 1485,147, 184, 119, 1170, 85, 775 cm -1. MS (EI, 70 ev) m/z (%): 5.0 (19), 4.0 (100) [M + ], 3. (13), 09. (63), 08.3 (15), 194. (4), 193. (14). HRMS (EI-TF) calcd. for C 16 H 16 : 4.101; found Phenoxy-3-((E)-1-phenylprop-1-en--yl)benzene (3fa) S1

13 Compound 3fa was prepared following general procedure A, starting from -phenoxybenzoic acid (1f) (109 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3fa was obtained as colorless liquid (130 mg, 0.49 mmol, 99 %). Compound 3fa was prepared following general procedure B, starting from -phenoxybenzoic acid (1f) (18 mg, 1 mmol) and 1-phenyl-1-propyne (a) (59 mg, 64 µl, 0.5 mmol). After purification, 3fa was obtained as colorless liquid (110 mg, 0.4 mmol, 84 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 8 H) (m, 1 H) 7. (s, 1 H) (m, 1 H) 7.06 (d, J=8.3 Hz, H) (m, 1 H) 6.86 (s, 1 H).7 (s, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), (s), (s), 19.7 (s), 19.5 (s), 19.1 (s), 18. (s), 18. (s), 18.1 (s), 16.6 (s), 15.3 (s), 13.1 (s), 11.0 (s), (s), (s), (s), 77.3 (s), 77. (s), 76.7 (s), 17.4 (s) ppm. IR: ṽ = 305, 301, 915, 1591, 157, 1485, 1431, 17, 118, 1163,1071, 1086, 916, 749 cm -1. MS (EI, 70 ev) m/z (%): 87.1 (19), 86. (100) [M + ], 71.3 (40), 193. (0), 178. (0), 77 (15). HRMS (EI-TF) calcd. for C 1 H 18 : ; found Hydroxy-3-((Z)-1-phenylprop-1-en--yl)benzene (3ga) Compound 3ga was prepared following general procedure, starting from -hydroxybenzoic acid (1g) (90 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3ga was obtained as a colorless liquid as the corresponding methylether after treatment with MeI (5 eq.) and K C 3 ( eq.) at 60 C in NMP (93 mg, 0.4 mmol, 83%). S13

14 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 4 H) (m, H) (m, 1 H) (m, 1 H) (m, H) 3.83 (s, 3 H).5 (d, J=1.3 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), 138. (s), (s), 19. (s), 19.1 (s), 18. (s), 17.8 (s), 16.5 (s), (s), 11.4 (s), 11.0 (s), 77.3 (s), 76.7 (s), 55.3 (s), 17.5 (s) ppm. IR: ṽ = 30, 996, 941, 834, 1597, 1576, 1485,147, 184, 119, 1170, 85, 775 cm -1. MS (EI, 70 ev) m/z (%): 5.0 (19), 4.0 (100) [M + ], 3. (13), 09. (63), 08.3 (15), 194. (4), 193. (14). HRMS (EI-TF) calcd. for C 16 H 16 : 4.101; found (3-((E)-1-phenylprop-1-en--yl)phenyl)ethanone (3ha) CAS [ ] Compound 3ha was prepared following general procedure, starting from -acetylbenzoic acid (1h) (83 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3ha was obtained as colorless liquid (91 mg, 0.38 mmol, 77 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 1 H) 7.89 (dt, J=7.6, 1.5 Hz, 1 H) 7.74 (dt, J=8.1, 1.5 Hz, 1 H) 7.49 (t, J=7.7 Hz, 1 H) (m, 4 H) 7.9 (dt, J=6.0,.9 Hz, 1 H) (m, 1 H).66 (s, 3 H).33 (d, J=1.5 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), 137. (s), (s), (s), 19.1 (s), 18.7 (s), 18.6 (s), 18. (s), 18. (s), 17.1 (s), 16.7 (s), 15.7 (s), 77.3 (s), 77.0 (s), 76.7 (s), 6.8 (s), 17.5 (s) ppm. IR: ṽ = 3061, 30, 1681, 1596, 1577, 1491, 143, 1355, 183, 159, 18, 79, 750, 69 cm -1. MS (EI, 70 ev) m/z (%): 37.1 (6), 36. (100) [M + ], 1. (64), (54), 178. (39), 50.1 (13), 43.1 (57). HRMS (EI-TF) calcd. for C 17 H 16 : ; found Phenyl-(3-((E)-1-phenylprop-1-en--yl)phenyl)methanone (3ia) S14

15 Compound 3ia was prepared following general procedure, starting from -benzoylbenzoic acid (1i) (83 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3ia was obtained as colorless solid (131 mg, 0.44 mmol, 88 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = 7.99 (t, J=1.9 Hz, 1 H) 7.86 (dd, J=8.4, 1.4 Hz, H) 7.76 (dt, J=7.8, 1.6 Hz, 1 H) 7.70 (dt, J=7.7, 1.4 Hz, 1 H) (m, 1 H) (m, 3 H) (m, 4 H) (m, H) 6.90 (d, J=1.5 Hz, 1 H).3 (d, J=1.5 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), 144. (s), (s), (s), (s), (s), 13.5 (s), (s), 19.9 (s), 19.9 (s), 19.1 (s), 18.9 (s), 18.7 (s), 18.3 (s), 18. (s), 18. (s), 17.4 (s), 16.7 (s), 77.3 (s), 77. (s), 76.7 (s), 17.5 (s) ppm. m.p. = C IR: ṽ = 3059, 304, 1656, 1595, 1576, 1491, 1446, 1337, 1317, 184, 139, 1177, 1144, 1074, 948, 91 cm -1. MS (EI, 70 ev) m/z (%):99.1 (), 98 (100) [M + ], 80.1 (3), 1.1 (10), (7), 105 (67), 77 (48). HRMS (EI-TF) calcd. for C H 18 : ; found (Methylsulfonyl)-3-((E)-1-phenylprop-1-en-yl)benzene (3ja) Compound 3ja was prepared following general procedure A, starting from - methylsulfonylbenzoic acid (1j) (83. mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3ja was obtained as colorless liquid (130 mg, 0.45 mmol, 95 %). S15

16 Compound 3ja was prepared following general procedure B, starting from - methylsulfonylbenzoic acid (1j) (168 mg, 1 mmol) and 1-phenyl-1-propyne (a) (59 mg, 64 µl, 0.5 mmol). After purification, 3ja was obtained as colorless liquid (90 mg, 0.31 mmol, 66 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = 8.10 (t, J=1.9 Hz, 1 H) 7.87 (dt, J=7.8, 1.6 Hz, 1 H) 7.81 (dt, J=8.1, 1.5 Hz, 1 H) 7.59 (t, J=7.8 Hz, 1 H) (m, 4 H) 7.30 (d, J=6.8 Hz, 1 H) (m, 1 H) 3.11 (s, 3 H).3 (d, J=1.5 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), (s), (s), 19.8 (s), 19.4 (s), 19.1 (s), 18.3 (s), 17.0 (s), 15.7 (s), 14.7 (s), 77.3 (s), 76.7 (s), 44.5 (s), 17.4 (s) ppm. IR: ṽ = 3059, 301, 97, 197, 114,1097, 1086, 955, 760, 744 cm -1. MS (EI, 70 ev) m/z (%): 7.0 (100) [M + ], 85.0 (63), 68.9 (47), 57.0 (46), 54.9 (68), 43.0 (61), 41.0 (7). HRMS (EI-TF) calcd. for C 16 H 16 S: ; found Fluoro-3-((Z)-1-phenylprop-1-en--yl)benzene (3ka) Compound 3ka was prepared following general procedure, starting from -fluorobenzoic acid (1k) (71 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3ka was obtained as colorless liquid (86 mg, 0.41 mmol, 81 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 6 H) (m, 1 H) (m, 1 H) (m, 1 H) 6.87 (s, 1 H).8 (d, J=1.3 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = 16.9 (d, J=44.3 Hz) 146. (d, J=7.3 Hz) (s) 136. (d, J=.7 Hz) 19.7 (d, J=8. Hz) 19.1 (s) 18.5 (s) 18. (s) 16.7 (s) 11.6 (d, J=.7 Hz) (d, J=0.89 Hz) 11.9 (d, J=1.8 Hz) 17.4 (s) ppm. 19 F-NMR (CDCl 3, 376 MHz): δ = ppm. IR: ṽ = 980, 1718, 1371, 107, 1157,109, 781 cm -1. S16

17 MS (EI, 70 ev) m/z (%):13.0 (15), 1.1 (100) [M + ], 197. (6), 196. (19), 177. (16), 115. (13), 50.0 (1). HRMS (EI-TF) calcd. for C 15 H 13 F: ; found ((E)--(3-hydroxyphenyl)prop-1-enyl)benzene (3la) Compound 3la was prepared following general procedure, starting from 4-hydroxybenzoic acid (1l) (70 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3la was obtained as colorless liquid as the corresponding methylether after treatment with MeI (5 eq.) and K C 3 ( eq.) at 60 C in NMP (79 mg, 0.36 mmol, 80%,). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 4 H) (m, H) (m, 1 H) (m, 1 H) (m, H) 3.86 (s, 3 H).8 (d, J=1.3 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), 138. (s), (s), 19. (s), 19.1 (s), 18. (s), 17.8 (s), 16.5 (s), (s), 11.4 (s), 11.0 (s), 77.3 (s), 76.7 (s), 55.3 (s), 17.5 (s) ppm. IR: ṽ = 30, 996, 941, 834, 1597, 1576, 1485,147, 184, 119, 1170, 85, 775 cm -1. MS (EI, 70 ev) m/z (%): 5.0 (19), 4.0 (100) [M + ], 3. (13), 09. (63), 08.3 (15), 194. (4), 193. (14). HRMS (EI-TF) calcd. for C 16 H 16 : 4.101; found ((E)--m-tolylprop-1-enyl)benzene (3ma) CAS [ ] S17

18 Compound 3ma was prepared following general procedure A, starting from 4-methylbenzoic acid (1m) (75.1 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3ma was obtained as colorless liquid (65 mg, 0.31 mmol, 6 %). Compound 3ma was prepared following general procedure B, starting from 4-methylbenzoic acid (1m) (150. mg, 1 mmol) and 1-phenyl-1-propyne (a) (59 mg, 64 µl, 0.5 mmol). After purification, 3ma was obtained as colorless liquid (68 mg, 0.33 mmol, 64 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 6 H) (m, H) 7.0 (d, J=7.0 Hz, 1 H) 6.73 (d, J=1.3 Hz, 1 H).30 (s, 3 H).18 (d, J=1.5 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), (s), 19.1 (s), 18. (s), 18.1 (s), 17.9 (s), 17.5 (s), 16.8 (s), 16.4 (s), 13.1 (s), 77.3 (s), 76.7 (s), 1.5 (s), 17.5 (s) ppm. IR: ṽ = 301, 917, 1600, 158, 1499, 144, 1376, 859, 779, 754, 694 cm -1. MS (EI, 70 ev) m/z (%):09.1 (16), 08.1 (100) [M + ], 194. (13), (85), 178. (7), (1), 89. (1). HRMS (EI-TF) calcd. for C 16 H 16 : ; found ((E)--(3-fluorophenyl)prop-1-enyl)benzene (3na) Compound 3na was prepared following general procedure A, starting from 4-fluorobenzoic acid (1n) (71 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3na was obtained as colorless liquid (60 mg, 0.41 mmol, 56 %). Compound 3na was prepared following general procedure B, starting from 4-fluorobenzoic acid (1n) (14 mg, 1 mmol) and 1-phenyl-1-propyne (a) (59 mg, 64 µl, 0.5 mmol). After purification, 3na was obtained as colorless liquid (75 mg, 0.36 mmol, 71 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 1 H) (m, 3 H) (m, H) (m, 3 H) (m, 1 H) 6.88 (s, 1 H).8 (d, J=1.3 Hz, 3 H) ppm. S18

19 13 C-NMR (CDCl 3, 101 MHz): δ = 16.9 (d, J=44.3 Hz) 146. (d, J=7.3 Hz) (s) 136. (d, J=.7 Hz) 19.7 (d, J=8. Hz) 19.1 (s) 18.5 (s) 18. (s) 16.7 (s) 11.6 (d, J=.7 Hz) (d, J=0.89 Hz) 11.9 (d, J=1.8 Hz) 17.4 (s) ppm. 19 F-NMR (CDCl 3, 376 MHz): δ = ppm. IR: ṽ = 980, 1718, 1371, 107, 1157,109, 781 cm -1. MS (EI, 70 ev) m/z (%): 13.0 (15), 1.1 (100) [M + ], 197. (6), 196. (19), 177. (16), 115. (13), 50.0 (1). HRMS (EI-TF) calcd. for C 15 H 13 F: ; found (E)--(3-bromophenyl)prop-1-enyl)benzene (3oa) CAS [ ] Compound 3oa was prepared following general procedure, starting from 4-bromobenzoic acid (1o) (103 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3oa was obtained as colorless liquid (78 mg, 0.9 mmol, 57 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = 7.68 (t, J=1.9 Hz, 1 H) (m, H) (m, 4 H) (m, H) 6.84 (s, 1 H).7 (d, J=1.3 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), (s), 19.8 (s), 19.1 (s), 18.8 (s), 18. (s), 16.8 (s), 14.6 (s), 1.5 (s), 77.3 (s), 76.7 (s), 17.4 (s) ppm. IR: ṽ = 3060, 301, 1589, 1558, 1474,1441, 147, 106, 863, 777, 74, 69 cm -1. MS (EI, 70 ev) m/z (%): 75.0 (18), 74.0 (100) [M + ], 73.0 (18), 7.1 (96), 59.1 (18), (33), 178. (60). HRMS (EI-TF) calcd. for C 15 H Br: 7.001; found calcd. for C 15 H Br: ; found (E)--(4-bromophenyl)prop-1-enyl)benzene (3pa) CAS [ ] S19

20 Compound 3pa was prepared following general procedure, starting from 3-bromobenzoic acid (1p) (103 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3pa was obtained as colorless solid (58 mg, 0.1 mmol, 43 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, H), (m, 5 H), (m, 1 H), 6.81 (s, 1 H),.4 (d, J=1.3 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = 14.8 (s), (s), 136. (s), (s), 19.1 (s), 18. (s), 18.1 (s), 17.6 (s), 16.7 (s), 11.0 (s), 17.3 (s) ppm. m.p. = C IR: ṽ = 3060, 301, 1589, 1558, 1474,1441, 147, 106, 863, 777, 74, 69 cm -1. MS (EI, 70 ev) m/z (%): 75.0 (18), 74.0 (100) [M + ], 73.0 (18), 7.1 (96), 59.1 (18), (33), 178. (60). HRMS (EI-TF) calcd. for C 15 H Br: 7.001; found calcd. for C 15 H Br: ; found ((E)-1-phenylprop-1-en--yl)benzonitrile (3qa) NC Compound 3qa was prepared following general procedure, starting from 3-cyanobenzoic acid (1q) (75.1 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3qa was obtained as colorless solid (46 mg, 0.1 mmol, 4 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 4 H), (m, 4 H), (m, 1 H), 6.93 (s, 1 H),.30 (d, J=1.3 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), 13. (s), (s), 19.1 (s), 18.3 (s), 17.1 (s), 16.6 (s), (s), (s), 17.1 (s) ppm. m.p. = C S0

21 IR: ṽ = 950, 6, 1598, 1501, 1444, 1407, 1377, 1180, 1117, 1080, 106, 84, 87, 758, 711, 696 cm -1. MS (EI, 70 ev) m/z (%): 0. (5), 19.3 (100) [M + ], 18.3 (15), 04.3 (78), 03.4 (14), (14), 50.1 (14). HRMS (EI-TF) calcd. for C 16 H 13 N: ; found ,-dihydroxy-5-((E)-1-phenylprop-1-en--yl)benzene (3ra) Compound 3ra was prepared following general procedure, starting from,4-dihydroxybenzoic acid (1r) (103 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3ra was obtained as colorless liquid as the corresponding methylether after treatment with MeI (5 eq.) and K C 3 ( eq.) at 60 C in NMP (104 mg, 0.9 mmol, 8 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 4 H) (m, 1 H) (m, 1 H) 6.69 (d, J=.3 Hz, H) (m, 1 H) 3.85 (s, 6 H).7 (d, J=1.5 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), (s), 19.5 (s), 18.5 (s), 18. (s), 16.8 (s), (s), 99.4 (s), 77.6 (s), 77.5 (s), 77.3 (s), 55.7 (s), 17.9 (s) ppm. IR: ṽ = 997, 943, 837, 1588, 1454,141, 1348, 139, 103, 115, 1067, 1048, 833, 751, 699 cm -1. MS (EI, 70 ev) m/z (%):55.3 (19), 54. (100) [M + ], 53.3 (3), 39.3 (56), 4.3 (14), 3.4 (1), 08.3 (14). HRMS (EI-TF) calcd. for C 17 H 18 : ; found ,-dimethoxy-5-((E)-1-phenylprop-1-en--yl)benzene (3sa) S1

22 Compound 3sa was prepared following general procedure, starting from,4-dimethoxybenzoic acid (1s) (93 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3sa was obtained as colorless liquid (78 mg, 0.9 mmol, 61 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 4 H) (m, 1 H) (m, 1 H) 6.69 (d, J=.3 Hz, H) (m, 1 H) 3.85 (s, 6 H).7 (d, J=1.5 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), (s), 19.5 (s), 18.5 (s), 18. (s), 16.8 (s), (s), 99.4 (s), 77.6 (s), 77.5 (s), 77.3 (s), 55.7 (s), 17.9 (s) ppm. IR: ṽ = 997, 943, 837, 1588, 1454,141, 1348, 139, 103, 115, 1067, 1048, 833, 751, 699 cm -1. MS (EI, 70 ev) m/z (%):55.3 (19), 54. (100) [M + ], 53.3 (3), 39.3 (56), 4.3 (14), 3.4 (1), 08.3 (14). HRMS (EI-TF) calcd. for C 17 H 18 : ; found ,3-Dimethyl-5-((Z)-1-phenylprop-1-en--yl)benzene (3ta) Compound 3ta was prepared following general procedure, starting from,4-dimethylbenzoic acid (1t) (76 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3ta was obtained as colorless liquid (93 mg, 0.4 mmol, 84 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = 7.8 (d, J=1.8 Hz, 4 H) 7.14 (s, 1 H) 7.06 (s, H) 6.86 (s, 1 H) 6.7 (d, J=1.3 Hz, 1 H).7 (s, 6 H).18 (d, J=1.5 Hz, 3 H) ppm. S

23 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), (s), 19.1 (s), 18.8 (s), 18.8 (s), 18.5 (s), 18.1 (s), 17.8 (s), 17.4 (s), 16.3 (s), 16.0 (s), 15.7 (s), 13.9 (s), 77.3 (s), 76.7 (s), 1.4 (s), 1.3 (s), 17.6 (s) ppm. IR: ṽ = 301, 916, 861, 1599, 1493, 1443, 1375, 841, 749, 696 cm -1. MS (EI, 70 ev) m/z (%):3.1 (19),.1 (100) [M + ], 08.3 (9), 07.3 (5), 19.3 (17), 115. (14), 91. (9). HRMS (EI-TF) calcd. for C 17 H 18 :.1409; found ((E)-1-phenylprop-1-en--yl)naphthalene (3ua) CAS [ ] Compound 3ua was prepared following general procedure, starting from -naphthoic acid (1u) (88 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3ua was obtained as colorless solid (50mg, 0.0 mmol, 40 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = 7.97 (d, J=1.3 Hz, 1 H), (m, 3 H), (m, 1 H), (m, 6 H), 7.30 (td, J=6.0,.9 Hz, 1 H), 7.04 (d, J=1.0 Hz, 1 H),.4 (d, J=1.3 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), 137. (s), (s), 13.7 (s), 19.3 (s), 18.3 (s), 18. (s), 18. (s), 17.8 (s), 17.6 (s), 16.6 (s), 16. (s), 15.8 (s), 14.7 (s), 14.4 (s), 17.5 (s) ppm. m.p. = C IR: ṽ = 3055, 1595, 1571, 1486, 1444, 1386, 175, 1130, 107, 853, 810, 74, 716, 695 cm -1. MS (EI, 70 ev) m/z (%): 45.1 (4), 44. (100) [M + ], 43.3 (11), 30.3 (11), 9.3 (61), 8.5 (0), 115. (9). HRMS (EI-TF) calcd. for C 19 H 16 : 44.15; found (E)-1-phenylprop-1-en--yl)quinoline (3va) S3

24 N Compound 3va was prepared following general procedure, starting from 6-quinolinecarboxylic acid (1v) (89.3 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3va was obtained as orange solid (44mg, 0.18 mmol, 36 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = 8.93 (dd, J=4.1, 1.6 Hz, 1 H), 8.4 (d, J=1.0 Hz, 1 H), 8.16 (ddd, J=8.3, 1.5, 0.8 Hz, 1 H), 7.8 (d, J=1.3 Hz, H), (m, 5 H), 7.30 (td, J=5.8,.8 Hz, 1 H), 7.10 (d, J=1.3 Hz, 1 H),.43 (d, J=1.3 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), (s), (s), (s), 19.3 (s), 19. (s), 18. (s), 17.5 (s), 17.4 (s), 16.8 (s), 16.0 (s), 15.1 (s), 10.8 (s), 17.3 (s) ppm. m.p. = C IR: ṽ = 301, 917, 340, 1740, 1614, 1593, 1495, 1441, 1383, 130, 835, 86, 753, 714, 693 cm -1. MS (EI, 70 ev) m/z (%): 45 (5), 44 (100) [M + ], 9.0 (1), 0 (3), 115.(4). HRMS (EI-TF) calcd. for C 18 H 15 N: ; found ((E--(3-methyl-4-nitrophenyl)prop-1-enyl)benzene (3wa) Compound 3wa was prepared following general procedure, starting from -methyl-3- nitrobenzoic acid (1w) (91 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) ( 88mg, 95 µl, 0.75 mmol). After purification, 3wa was obtained as yellow solid (69 mg, 0.7 mmol, 55 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 1 H) (m, H) (m, 4 H) 7.31 (d, J=6.8 Hz, 1 H) (m, 1 H).68 (s, 3 H).31 (d, J=1.5 Hz, 3 H) ppm. S4

25 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), (s), (s), (s), 130. (s), 19.1 (s), 18.3 (s), 17.1 (s), 15.0 (s), 14.3 (s), 77.3 (s), 76.7 (s), 1.0 (s), 17.3 (s) ppm. m.p. = 61-6 C IR: ṽ = 305, 997, 915, 858, 1599, 1578, 1510, 1488, 1445, 1337, 1813, 107, 1184, 1069, 870, 87, 760, 753, 701 cm -1. MS (EI, 70 ev) m/z (%):54. (19), 53.1 (100) [M + ], 38. (9), 36. (15), 06.3 (8), 19.3 (18), (11). HRMS (EI-TF) calcd. for C 16 H 15 N : ; found ((E)-1-phenylprop-1-en--yl)naphthalene (3xa) CAS [ ] Compound 3xa was prepared following general procedure, starting from 1-naphthoic acid (1x) (88 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) (88 mg, 95.7 µl, 0.75 mmol). After purification, 3xa was obtained as colorless solid (109 mg, 0.45 mmol, 89 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 1 H) (m, 3 H) 7.74 (dd, J=8.5,.0 Hz, 1 H) 7.49 (ddd, J=7.6, 5.5, 1.8 Hz, H) (m, 4 H) 7.9 (d, J=.8 Hz, 1 H) 7.03 (d, J=1.3 Hz, 1 H).4 (d, J=1.5 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), 137. (s), (s), 13.7 (s), 19. (s), 18. (s), 18. (s), 18.1 (s), 17.8 (s), 17.5 (s), 16.5 (s), 16. (s), 15.8 (s), 14.7 (s), 14.4 (s), 77.3 (s), 76.7 (s), 17.5 (s) ppm. m.p. = C IR: ṽ = 3055, 1595, 1571, 1486, 1444, 1386, 175, 1130, 107, 853, 810, 74, 716, 695 cm -1. MS (EI, 70 ev) m/z (%): 45.1 (4), 44. (100) [M + ], 43.3 (11), 30.3 (11), 9.3 (61), 8.5 (0), 115. (9). HRMS (EI-TF) calcd. for C 19 H 16 : 44.15; found S5

26 (E)-1, -diphenylprop-1-ene (3ya) [CAS: ] Compound 3ya was prepared following general procedure A, starting from benzoic acid (1y) (61 mg, 1 mmol) and 1-phenyl-1-propyne (a) (58 mg, 64 µl, 0.5 mmol). After purification, 3ya was obtained as colorless oil (39 mg, 0. mmol, 40 %). Compound 3ya was prepared following general procedure B, starting from benzoic acid (1y) (150. mg, 1 mmol) and 1-phenyl-1-propyne (a) (59 mg, 64 µl, 0.5 mmol). After purification, 3ya was obtained as colorless liquid (58 mg, 0.3 mmol, 60 %). 1 H-NMR (00 MHz, CDCl3): δ = (m, H), (m, 8 H), 6.85 (d, J=1.0 Hz, 1 H),.30 (d, J=1.3 Hz, 3 H) ppm. 13 C-NMR (CDCl3, 101 MHz): δ = (s), (s), (s), 19.1 (s), 18.3 (s), 18.1 (s), 17.7 (s), 17. (s), 16.4 (s), 16.0 (s), 17.5 (s) ppm. Analytical data correspond to those previously reported [1],[],[3] 1,,5-trimethoxy-3-((E)-1-phenylprop-1-en--yl)benzene (3za) Compound 3za was prepared following general procedure, starting from,4,5- trimethoxybenzoic aid (1z) (107 mg, 0.5 mmol) and 1-phenyl-1-propyne (a) ( 88mg, 95 µl, 0.75 mmol). After purification, 3za was obtained as colorless solid (86 mg, 0.30mmol, 60 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 4 H) (m, H) 6.59 (d, J=1.5 Hz, 1 H) 6.48 (d, J=3.0 Hz, 1 H) 6.40 (d, J=3.0 Hz, 1 H) 3.88 (s, 3 H) 3.83 (s, 3 H) 3.76 (s, 3 H).8 (d, J=1.5 Hz, 3 H) ppm. S6

27 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), (s), (s), 19.7 (s), 19.3 (s), 18.5 (s), 16.8 (s), (s), 99.3 (s), 77.6 (s), 77.3 (s), 61. (s), 56. (s), 55.9 (s), 19.5 (s) ppm. m.p. = C IR: ṽ = 939, 837, 1588, 148, 1463, 1419, 1338, 174, 14, 1199, 1174, 1157,1135, 1100, 1006, 830, 773, 749, 698 cm -1. MS (EI, 70 ev) m/z (%): 85. (0), 84.3 (100) [M + ], 69.3 (48), 53.3 (15), 41.3 (10), 103. (9), 91. (14) HRMS (EI-TF) calcd. for C 18 H 0 3 : ; found Ethyl (E)-3-(3-methoxyphenyl)-3-phenylprop--enoate (3 ab) CAS [ ] Compound 3 ab was prepared following general procedure A, starting from 4-methoxylbenzoic acid (1a) (77 mg, 0.5 mmol) and ethyl-3-phenylpropiolate (b) (133 mg, 17 µl, 0.75 mmol). After purification, 3 ab was obtained as colorless liquid (10 mg, 0.36 mmol, 7 %). Compound 3 ab was prepared following general procedure B, starting from 4-methoxylbenzoic acid (1a) (77 mg, 0.5 mmol) and ethyl-3-phenylpropiolate (b) (133 mg, 17 µl, 0.75 mmol). After purification, 3 ab was obtained as colorless liquid (58 mg, 0.1 mmol, 41 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 6 H), (m, 3 H), 6.90 (dd, J=8.,.6 Hz, 1 H), 4.9 (q, J=7.0 Hz, H), 3.85 (s, 3 H), 1. (t, J=7.0 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), (s), (s), (s), 19.7 (s), 18.4 (s), 18.3 (s), 18. (s), (s), (s), 11.0 (s), 61.3 (s), 55.3 (s), 13.9 (s) ppm. IR: ṽ = 967, 836, 1603, 1718, 1596, 1578, 1488, 1371, 187, 115, 1184, 1156, 103, 691 cm -1. S7

28 MS (EI, 70 ev) m/z (%): 83.0 (19), 8.0 (100) [M + ], 37. (11), 09. (30), (10), (1), (11). HRMS (EI-TF) calcd. for C 18 H 18 : 8.156; found (Z)--(3-Methoxyphenyl)-3-phenylprop--en-1-ol (3ac) CAS [ ] Compound 3ac was prepared following general procedure A, starting from 4-methoxylbenzoic acid (1a) (77 mg, 0.5 mmol) and 1-(3-hydroxyprop-1-ynyl)benzene (c) (105 mg, 110 µl, 0.75 mmol). After purification, 3ac was obtained as colorless liquid (96 mg, 0.4 mmol, 80 %). Compound 3ac was prepared following general procedure B, starting from 4-methoxylbenzoic acid (1a) (77 mg, 0.5 mmol) and 1-(3-hydroxyprop-1-ynyl)benzene (c) (105 mg, 110 µl, 0.75 mmol). After purification, 3ac was obtained as colorless liquid (63 mg, 0.6 mmol, 5 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 7 H), (m, 1 H), (m, 1 H), 6.99 (s, 1 H), 6.90 (ddd, J=8.,.6, 1.0 Hz, 1 H), 4.71 (s, H), 3.87 (s, 3 H), 1.6 (br. s, 1 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), 14.1 (s), (s), (s), (s), 19.7 (s), 18.9 (s), 18.4 (s), 17.4 (s), (s), (s), 11.5 (s), 60.4 (s), 55.3 (s) ppm. IR: ṽ = 339, 303, 938, 834, 1713, 1597, 1576, 1487, 1447, 186, 166, 18, 1169, 1033, 1010, 86, 777, 755, 694 cm -1. MS (EI, 70 ev) m/z (%): 41.0 (16), 40.0 (100) [M + ], 3.1 (30), (19), 11.0 (7). HRMS (EI-TF) calcd. for C 16 H 16 : ; found Ethyl (E)-3-(3-methylphenyl)-3-phenylprop--enoate (3 bb) CAS [ ] S8

29 Compound 3 bb was prepared following general procedure, starting from -methylbenzoic acid (1b) (69 mg, 0.5 mmol) and ethyl-3-phenylpropiolate (b) (133 mg, 17 µl, 0.75 mmol). After purification, 3 bb was obtained as colorless liquid (59 mg, 0. mmol, 44 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 4 H) (m, 4 H) 7.18 (ddd, J=4.6, 3.5, 1.5 Hz, 1 H) 7.05 (s, 1 H) 4.30 (q, J=7.0 Hz, H).40 (s, 3 H) 1. (t, J=7. Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), (s), (s), (s), 19.1 (s), 18.6 (s), 18.4 (s), 18. (s), 18. (s), 17.0 (s), 13.5 (s), 61.3 (s), 1.5 (s), 13.9 (s) ppm. IR: ṽ = 981, 1717, 160, 1495, 1446, 1371, 186,, 108, 1157, 1094, 109, 78, 75, 69 cm -1. MS (EI, 70 ev) m/z (%): 67.0 (19), 66.1 (100) [M + ], 19. (11), 193. (43), 178. (1), (1), (18). HRMS (EI-TF) calcd. for C 18 H 18 : ; found ((E)-3-Hydroxy-1-phenylprop-1-en--yl)-3-methylbenzene (3bc) CAS [ ] Compound 3bc was prepared following general procedure, starting from -methylbenzoic acid (1b) (69 mg, 0.5 mmol) and 1-(3-hydroxyprop-1-ynyl)benzene (c) (105 mg, 110 µl, 0.75 mmol). After purification, 3bc was obtained as colorless liquid (79 mg, 0.35 mmol, 70 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 6 H) (m, H) 7.17 (d, J=7.5 Hz, 1 H) 6.97 (s, 1 H) 4.7 (s, H).4 (s, 3 H) 1.63 (s, 1 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), (s), 18.9 (s), 18.6 (s), 18.5 (s), 18.4 (s), 17.4 (s), 17.3 (s), 13.7 (s), 10.0 (s), 60.4 (s), 1.6 (s) ppm. S9

30 IR: ṽ = 3360, 305, 301, 91, 1601, 1493, 1445, 1010, 999, 966, 78, 754, 69 cm -1. MS (EI, 70 ev) m/z (%): 5.1 (1), 4.1 (100) [M + ], 09. (15), 195. (13), 178. (11), 119 (70), 105 (40), 91 (36), 77 (0). HRMS (EI-TF) calcd. for C 16 H 16 : 4.101; found Methyl-3-((Z)-1-phenylbut-1-en--yl)benzene (3bd) Compound 3bd was prepared following general procedure, starting from -methylbenzoic acid (1b) (69 mg, 0.5 mmol) and 1-(but-1-ynyl)benzene (d) (97 mg, 109 µl, 0.75 mmol). After purification, 3bd was obtained as colorless solid (80 mg, 0.4 mmol, 70%). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 4 H), (m, 1 H), (m, 3 H), (m, 1 H), 6.69 (s, 1 H),.75 (q, J=7.4 Hz, H),.40 (s, 3 H), 1.07 (t, J=7.5 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), 14.7 (s), (s), (s), 18.9 (s), 18.7 (s), 18. (s), 17.9 (s), 17.8 (s), 17.4 (s), 16.5 (s), 13.7 (s), 3.3 (s), 1.6 (s), 13.5 (s) ppm. m. p. = C IR: ṽ = 300, 965, 1601, 1494, 1445, 1376, 864, 780, 753, 698 cm -1. MS (EI, 70 ev) m/z (%): 3.0 (1),.1 (100) [M + ], 08. (9), 07. (44), 193. (14), 19. (10), (6). HRMS (EI-TF) calcd. for C 17 H 18 :.1409; found Methyl-3-((Z)-1-phenylpent-1-en--yl)benzene (3be) S30

31 Compound 3be was prepared following general procedure, starting from -methylbenzoic acid (1l) (69 mg, 0.5 mmol) and 1-phenyl-1-pentyne (e) (110 mg, 115 µl, 0.75 mmol). After purification, 3be was obtained as colorless liquid (95 mg, 0.4 mmol, 80 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 4 H), (m, 4 H), (m, 1 H), 6.69 (s, 1 H), (m, H),.40 (s, 3 H), (m, H), 0.91 (t, J=7.4 Hz, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), 143. (s), (s), (s), 18.8 (s), 18. (s), 18. (s), 18.1 (s), 17.9 (s), 17.4 (s), 16.4 (s), 13.7 (s), 77.3 (s), 76.7 (s), 3. (s),.0 (s), 1.6 (s), 14.1 (s) ppm. IR: ṽ = 303, 958, 97, 1601, 1493, 1455, 1377, 1088, 781, 698 cm -1. MS (EI, 70 ev) m/z (%): 37.0 (1), 36.1 (100) [M + ], 08. (9), 07. (44), 193. (14), 19. (10), (6). HRMS (EI-TF) calcd. for C 18 H 0 : ; found ((E)-3-methoxy-1-phenylprop-1-en--yl)-3-methylbenzene (3bf) Compound 3lf was prepared following general procedure, starting from -methylbenzoic acid (1b) (69 mg, 0.5 mmol) and 1-(3-methoxyprop-1-ynyl)benzene (f) (110 mg, 115 µl, 0.75 mmol). After purification, 3bf was obtained as colorless liquid (66 mg, 0.8 mmol, 56 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 6 H) (m, H) (m, 1 H) 7.05 (s, 1 H) 4.39 (s, H) 3.40 (s, 3 H).41 (s, 3 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s), (s), (s), 137. (s), 13.4 (s), 19.0 (s), 18.3 (s), 18.3 (s), 18. (s), 17. (s), 17.1 (s), 13.4 (s), 70.1 (s), 58.1 (s), 1.6 (s) ppm. IR: ṽ = 30, 9, 1603, 1493, 1446, 1193, 1094, 95, 785, 69 cm -1. MS (EI, 70 ev) m/z (%):38.1 (100) [M + ], 37. (59), 3. (75), 07. (1), 06. (1), 115. (34), 91. (). HRMS (EI-TF) calcd. for C 17 H 18 : ; found S31

32 (Z)--(3-Fluorophenyl-3-phenylprop--en-1-ol (3nc) F H Compound 3nc was prepared following general procedure A, starting from 4-fluorolbenzoic acid (1n) (71.5 mg, 0.5 mmol) and 1-(3-hydroxyprop-1-ynyl)benzene (c) (105 mg, 110 µl, 0.75 mmol). After purification, 3nc was obtained as colorless liquid (83 mg, 0.36 mmol, 73 %). Compound 3nc was prepared following general procedure B, starting from 4-fluorolbenzoic acid (1n) (71.5 mg, 0.5 mmol) and 1-(3-hydroxyprop-1-ynyl)benzene (c) (105 mg, 110 µl, 0.75 mmol). After purification, 3nc was obtained as colorless liquid (75 mg, 0.33 mmol, 66 %). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, 8 H), (m, H), 4.70 (s, H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (d, J=46.1 Hz) (d, J=7.3 Hz) (d, J=.7 Hz) (s) 13. (s) (d, J=8. Hz) 18.9 (s) 18.5 (s) 17.7 (s) 1. (d, J=.7 Hz) (d, J=1.8 Hz) (d, J=.7 Hz) 60.3 (s) ppm. 19 F-NMR (CDCl 3, 376 MHz): δ = ppm. IR: ṽ = 3333, 304, 338, 1741, 1609, 1580, 1484, 1443, 163, 19, 1174, 1158, 1011, 968, 90, 864, 780, 756, 694 cm -1. MS (EI, 70 ev) m/z (%): 8.8 (15), 7.9 (100) [M + ], 11.0 (3), 13.0 (10), (33), 91.0 (13). HRMS (EI-TF) calcd. for C 15 H 13 F: ; found Synthesis of [Ru(4-Me-benzoato - -C 6, 1 )(hexamethylbenzene)(pyridine)] (7a) S3

33 Compound 7a was synthesized following the literature reported procedure [4], starting from potassium 4-methoxy benzoate (1a) (85 mg, 1.5 mmol), [Ru(hexaymethylbenzene)Cl ] (334 mg, 0.5 mmol), pyridine (79 mg, 81μL, 1 mmol) and trimethylamine (715 mg, 983 μl, 7 mmol). 7a was isolated as a yellow soid (148 mg, 60%). 1 H-NMR (400 MHz, CDCl 3 ): δ = (m, H), 7.46 (tt, J=7.7, 1.6 Hz, 1 H), 7.38 (d, J=.5 Hz, 1 H), 7.35 (d, J=8.3 Hz, 1 H), (m, H), 6.44 (dd, J=8.3,.5 Hz, 1 H), 3.86 (s, 3 H), 1.94 (s, 18 H) ppm. 13 C-NMR (CDCl 3, 101 MHz): δ = (s) (s) 153. (s) (s) (s) 19.1 (s) 14.4 (s) 10.0 (s) 11.7 (s) (s) 93.4 (s) 54.9 (s) 15. (s) ppm. m.p. = 144 C, decomp. IR: ṽ = 917, 1600, 1573, 1445, 1430, 1385, 1308, 14, 1, 107, 1167, 1144, 1067, 106, 855, 777, 761, 696 cm -1. MS (ESI): m/z = calcd. for C 5 H 9 3 NRu+H + : 494.1; found References [1] J. Cotter, A.-M. L. Hogan, D. F. Shea, rg. Lett.s 007, 9, [] J. Shi, E. Negishi, J. rganomet. Chem. 003, 687, [3] D. M. Hodgson, M. J. Fleming, S. J. Stanway, J. rg. Chem. 007, 7, [4] S. Warratz, C. Kornhaaß, A. Cajaraville, B. Niepötter, D. Stalke, L. Ackermann, Angew. Chem. Int. Ed. 015, 54, S33

34 NMR spectra 3aa esp M06(m) M07(d*) M03(m) 10a M05(m) M04(m) 6 M01(d) H 3 C esp M1(s) M11(s) 10a M10(s) M13(s) M09(s) 6 M14(s*) M08(s) M04(s) H 3 C M07(s) M06(s) M05(s) M16(s) M15(s) M01(s) S34

35 3ba AHM-647-H r.esp M05(m) M06(m) M01(d) M04(m) M03(m) C r.esp M10(s) M04(s) M05(s) M07(s) M06(s) M09(s) M08(s) M1(s) M14(s) M13(s) M11(s) M01(s) S35

36 3ca esp M08(m) M06(s*) M05(s*) M07(d*) M04(d*) M03(d*) M0(d) M01(t) a esp M04(s) M1(s) M05(s) 8 M07(s) M13(s*) M11(s) M10(s) a M15(s*) M09(s) M14(s) M08(s) M06(s) M17(s*) M16(s) M01(s) S36

37 3da AHm-644-H-(31).esp M07(m) M03(m) M06(m) M05(d*) M04(d*) M08(s*) M0(d) M01(dd) H 311a C 10a esp M04(s) C H M14(s) M1(s) M11(s) M07(s) M13(s) M10(s) M09(s) M16(s) M08(s) M15(s) M06(s) M05(s) M17(s) M01(s) S37

38 3ea esp M06(m) M07(m) M03(m) M05(m) M04(m) M01(d) a esp M1(s) M10(s) M11(s) M13(s) M09(s) M14(s) M08(s) M04(s) a M07(s) M06(s) M05(s) M15(s) M01(s) M16(s) S38

39 3fa AHM65-10-H().esp M08(m) M03(m) M05(m) M04(d) M06(s) M07(m) M01(s) esp M04(s) 8 10 M16(s) M15(s) M13(s) M05(s) M11(s) M17(s) M08(s) M18(s) M14(s*) M07(s) M19(s) M1(s) M06(s) M01(s) M(s*) M1(s*) M0(s*) S39

40 3ga esp M06(m) M07(m) M03(m) M05(m) M04(m) M01(d) esp M1(s) M11(s) M10(s) M13(s) M09(s) M14(s) M08(s) M04(s) M07(s) M06(s) M05(s) M16(s) M15(s) M01(s) S40

41 3ha ESP.66 M08(m) M07(m) M09(m) 7.39 H 3 C M01(d) M04(m) M06(ddd) M05(dt) esp M1(s) M10(s) M07(s) M06(s) M13(s) M16(s) M11(s) M04(s) M05(s) M15(s) M09(s*) M17(s) M08(s) M19(s*) M18(s*) M0(s*) M01(s*) S41