Supporting Information

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1 Supporting Information Ligand-Controlled Palladium-Catalyzed Alkoxycarbonylation of Allenes: Regioselective Synthesis of α,β- and β,γ-unsaturated Esters Jie Liu, Qiang Liu,*, Robert Franke,, Ralf Jackstell, and Matthias Beller*, Leibniz-Institut für Katalyse e.v. an der Universität Rostock, Albert-Einstein-Str. 29a, Rostock, Germany Evonik Industries AG, Paul-Baumann-Str. 1, Marl, Germany Lehrstuhl für Theoretische Chemie, Bochum, Germany Corresponding Author

2 Table of Contents General Considerations... 2 Experimental sections Preparation of Substrates General procedure for the synthesis of Kinetic progress measurement for 3a: procedure for the deuterium labelling experiment: procedure for the controlling experiments: General procedure for the synthesis of 4: procedure for the deuterium labelling experiment: Kinetic progress procedure for 4a: Detailed optimization for the synthesis of 3a: Detailed optimization for the synthesis of 4a:... 9 Characterization of products References NMR spectra of products S1

3 General Considerations All commercial reagents were ordered from Alfa Aesar, Aldrich, TCI or Strem. Unless otherwise statement, commercial reagents were used without purification. Air- and moisture-sensitive syntheses were performed under argon atmosphere in heating gun vacuum dried glassware. Analytical data of literature known compounds were in accord with reported data. NMR spectra were recorded on Bruker Avance 300 (300 MHz) NMR spectrometers. Multiplets were assigned as s (singlet), d (doublet), t (triplet), dd (doublet of doublet), m (multiplet) and br. s (broad singlet). All measurements were carried out at room temperature unless otherwise stated. Electron impact (EI) mass spectra were recorded on AMD 402 mass spectrometer (70 ev). High resolution mass spectra (HRMS) were recorded on Agilent 6210 Time-of-Flight LC/MS (Agilent) with electrospray ionization (ESI). The data are given as mass units per charge (m/z) and intensities of signals are given in brackets. For GC analyses, HP 6890 chromatograph with a 29 m HP5 column was used. S2

4 Experimental sections 1. Preparation of Substrates (1). The aliphatic allenes: Cyclohexylallene, ethyl 2,3-butadienoate, 3-methyl-1,2-butadiene are commercial available and bought from sigma-aldrich. 1,2-Butadiene is provided by Evonik Industries AG. (2). The aryl-substituted allenes are synthesis according to the known literature. 1 (3). All the alcohols are commercial available and bought from sigma-aldrich, TCI, Alfa-Aeser or Acros. 2. General procedure for the synthesis of 3 A vial (4 ml) was charged with Pd(OAc) 2 (2.2 mg, 1.0 mol%), Xantphos (11.6 mg, 2.0 mol%), PTSA H 2 O (7.6 mg, 4.0 mol%) and a stirring bar was added. Then, allenes 1 (1.0 mmol) and alcohols 2 (1.2 mmol) * and toluene (2 ml) were injected by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 ml) of the 4560 series from Parr Instruments under argon atmosphere. At room temperature, the autoclave was flushed with CO three times, pressurized with CO to 40 bar. The reaction was performed for 20 h at 110 o C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released and isooctane (100 ul) (internal standard) was added to the solution. The yield and selectivity were measured by GC analysis. After removing the solvent by vacuum, the residue was directly purified by flash chromatography on silica gel (eluent: pentane/ethyl acetate = 50/1) to give the desired product 3. *4.0 mmol alcohol was used for 3g, 3h, 3k, 3l *condition for 3l: 1 (1.0 mmol), 2 (4.0 mmol), Pd(OAc) 2 (1.0 mol%), Xantphos (2.0 mol%), PTSA (4.0 mol%), CO (80 bar), toluene (2 ml), 130 o C, 20 h. Procedure for the 3i: A 25 ml autoclave was charged under argon atmosphere with Pd(cod)Cl 2 (0.1 mol%), Xantphos (0.2 mol%), PTSA H 2 O (0.4 mol%). Then, n-butanol (20 mmol) and toluene (10.0 ml) were injected by syringe. Then the autoclave was cooled with dry ice. 1,2-butadiene (20-25 mmol) was condensed in a separate pressure cylinder (75 ml, mass control) and this defined amount of 1,2-butadiene was then condensed into the cooled autoclave. Then, the autoclave was pressurized with 80 bar CO at room temperature. The reaction was carried out for 20 h at 130 o C. After the reaction time, the autoclave was cooled down to room temperature and the pressure was released and isooctane (0.5 ml) (internal standard) was added to the solution. The yield and selectivity were measured by GC analysis. After removing the solvent by vacuum, the residue was directly purified by flash chromatography on silica gel (eluent: pentane/ethyl acetate = 50/1) to give the desired product. S3

5 Procedure for the 3m: With 0.1 mol% Pd: A 25 ml autoclave was charged under argon atmosphere with Pd(cod)Cl 2 (0.1 mol%), Xantphos (0.2 mol%), PTSA H 2 O (0.4 mol%). Then, methanol (20 mmol) and toluene (10.0 ml) were injected by syringe. Then the autoclave was cooled with dry ice. 1,2-butadiene (20-25 mmol) was condensed in a separate pressure cylinder (75 ml, mass control) and this defined amount of 1,2-butadiene was then condensed into the cooled autoclave. Then, the autoclave was pressurized with 80 bar CO at room temperature. The reaction was carried out for 20 h at 130 o C. After the reaction time, the autoclave was cooled down to room temperature and the pressure was released and isooctane (0.5 ml) (internal standard) was added to the solution. The yield and selectivity were measured by GC analysis. With mol% Pd: A 25 ml autoclave was charged under argon atmosphere with Pd(cod)Cl 2 (0.025 mol%), Xantphos (0.05 mol%), PTSA H 2 O (0.1 mol%). Then, methanol (20 mmol) and toluene (10.0 ml) were injected by syringe. Then the autoclave was cooled with dry ice. 1,2-butadiene (20-25 mmol) was condensed in a separate pressure cylinder (75 ml, mass control) and this defined amount of 1,2-butadiene was then condensed into the cooled autoclave. Then, the autoclave was pressurized with 80 bar CO at room temperature. The reaction was carried out for 72 h at 130 o C. After the reaction time, the autoclave was cooled down to room temperature and the pressure was released and isooctane (0.5 ml) (internal standard) was added to the solution. The yield and selectivity were measured by GC analysis. Procedure for the 6m: A 25 ml autoclave was charged under argon atmosphere with Pd(acac) 2 (0.1 mol%), d t bpx (0.4 mol%), PTSA H 2 O (0.8 mol%). Then, 3m (10 mmol) and methanol (10 ml) were injected by syringe. Then, the autoclave was pressurized with 40 bar CO at room temperature. The reaction was carried out for 20 h at 100 o C. After the reaction time, the autoclave was cooled down to room temperature and the pressure was released and isooctane (0.5 ml) (internal standard) was added to the solution. The yield and selectivity were measured by GC analysis. 3. Kinetic progress measurement for 3a: A 25 ml autoclave was charged under argon atmosphere with Pd(OAc) 2 (1.0 mol%), Xantphos (2.0 mol%), PTSA H 2 O (4.0 mol%). Then, allene 1a (5.0 mmol), n-butanol (6.0 mmol), hexadecane (0.5 ml as internal) and toluene (10.0 ml) were injected by syringe. Then, the autoclave was pressurized with 40 bar CO at room temperature. The reaction was heated to 110 o C. Then samples were taken from the reaction mixture via a special valve on autoclave in a specific time and analyzed by GC. 4. procedure for the deuterium labelling experiment: TsOD D 2 O (90% d) was synthesized from the known literature 2 (1) A vial (4 ml) was charged with Pd(OAc) 2 (2.2 mg, 1.0 mol%), Xantphos (11.6 mg, 2.0 mol%), PTSA H 2 O (7.6 mg, 4.0 mol%) and a stirring bar was added. Then, allene 1a (1.0 mmol) and CD 3 OD (1.2 mmol) and toluene (2 ml) were injected by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 ml) of the 4560 series from Parr Instruments under argon S4

6 atmosphere. At room temperature, the autoclave was flushed with CO three times, pressurized with CO to 40 bar. The reaction was performed for 20 h at 110 o C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released and isooctane (100 ul) (internal standard) was added to the solution. The yield and selectivity were measured by GC analysis. After removing the solvent by vacuum, the residue was directly purified by flash chromatography on silica gel (eluent: pentane/ethyl acetate = 50/1) and the result was analyzed according to the 1 H NMR spectra. (2) A vial (4 ml) was charged with Pd(OAc) 2 (2.2 mg, 1.0 mol%), Xantphos (11.6 mg, 2.0 mol%), TsOD D 2 O (7.7 mg, 4.0 mol%) and a stirring bar was added. Then, allene 1a (1.0 mmol) and MeOH (1.2 mmol) and toluene (2 ml) were injected by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 ml) of the 4560 series from Parr Instruments under argon atmosphere. At room temperature, the autoclave was flushed with CO three times, pressurized with CO to 40 bar. The reaction was performed for 20 h at 110 o C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released and isooctane (100 ul) (internal standard) was added to the solution. The yield and selectivity were measured by GC analysis. After removing the solvent by vacuum, the residue was directly purified by flash chromatography on silica gel (eluent: pentane/ethyl acetate = 50/1) and the result was analyzed according to the 1H NMR spectra. 5. procedure for the controlling experiments: Experiment 5a to 3a: A vial (4 ml) was charged with Pd(OAc)2 (2.2 mg, 1.0 mol%), Xantphos (11.6 mg, 2.0 mol%), PTSA H2O (7.6 mg, 4.0 mol%) and a stirring bar was added. Then, 5a (1.0 mmol) and toluene (2 ml) were injected by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 ml) of the 4560 series from Parr Instruments under argon atmosphere. At room temperature, the autoclave was flushed with CO three times, pressurized with CO to 40 bar. The reaction was performed for 20 h at 110 o C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released and isooctane (100 ul) (internal standard) was added to the solution. The yield was measured by GC analysis. Entry 1 in table 2: Under the protection of argon, a 25 ml sealable glass tube equipped with a stir bar was charged with Pd(OAc) 2 (2.2 mg, 0.01 mmol), Xantphos (11.6 mg, 0.02 mmol), PTSA H 2 O (7.6 mg, 0.04 mmol). Then allene 1a (1 mmol) and n-buoh 2a (1.2 mmol), toluene (2 ml) were added sequentially. After the tube was fitted with a sealed cap, the reaction mixture was stirred at 110 o C for 15 min. The reaction solution was diluted with acetone and analyzed by gas chromatography using isooctane as internal standard and analyzed by GC. Entry 2 in table 2: Under the protection of argon, a 25 ml sealable glass tube equipped with a stir bar was charged with PTSA H 2 O (7.6 mg, 0.04 mmol). Then allene 1a (1 mmol) and n-buoh 2a (1.2 mmol), toluene (2 ml) were added sequentially. After the tube was fitted with a sealed cap, the reaction mixture was stirred at 110 o C for 15 min. The reaction solution was diluted with acetone and analyzed by gas chromatography using isooctane as internal standard and analyzed by GC. Entry 3 in table 2: Under the protection of argon, a 25 ml sealable glass tube equipped with a stir bar was charged with Pd(OAc) 2 (2.2 mg, 0.01 mmol), Xantphos (11.6 mg, 0.02 mmol). Then allene 1a (1 mmol) and n-buoh 2a (1.2 mmol), toluene (2 ml) were added sequentially. After the tube was fitted with a sealed cap, the reaction mixture was stirred at 110 o C for 15 min. The reaction solution was S5

7 diluted with acetone and analyzed by gas chromatography using isooctane as internal standard and analyzed by GC. 6. General procedure for the synthesis of 4: A vial (4 ml) was charged with Pd(OAc)2 (2.2 mg, 1.0 mol%), PPh 2 Py (15.8 mg, 6.0 mol%), TFA (9.1 mg, 8.0 mol%) and a stirring bar was added. Then, allenes 1 (1.0 mmol) and alcohols 2 (1.2 mmol) * and toluene (2 ml) were injected by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 ml) of the 4560 series from Parr Instruments under argon atmosphere. At room temperature, the autoclave was flushed with CO three times, pressurized with CO to 40 bar. The reaction was performed for 20 h at 110 o C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released and isooctane (100 ul) (internal standard) was added to the solution. The yield and selectivity were measured by GC analysis. After removing the solvent by vacuum, the residue was directly purified by flash chromatography on silica gel (eluent: pentane/ethyl acetate = 100/1) to give the desired product 4. *4.0 mmol alcohol was used for 4i and 4j Procedure for the 4k: A 25 ml autoclave was charged under argon atmosphere with Pd(cod)Cl 2 (0.2 mol%), PPh 2 Py (1.2 mol%), TFA (1.6 mol%). Then, n-butanol (20 mmol) and toluene (10.0 ml) were injected by syringe. Then the autoclave was cooled with dry ice. 1,2-butadiene (18 mmol) was condensed in a separate pressure cylinder (75 ml, mass control) and this defined amount of 1,2-butadiene was then condensed into the cooled autoclave. Then, the autoclave was pressurized with 80 bar CO at room temperature. The reaction was carried out for 20 h at 130 o C. After the reaction time, the autoclave was cooled down to room temperature and the pressure was released and isooctane (0.5 ml) (internal standard) was added to the solution. The yield and selectivity were measured by GC analysis. After removing the solvent by vacuum, the residue was directly purified by flash chromatography on silica gel (eluent: pentane/ethyl acetate = 100/1) to give the desired product. 7. procedure for the deuterium labelling experiment: TFA-d is commercial available in Sigma Aldrich (1) A vial (4 ml) was charged with Pd(OAc) 2 (2.2 mg, 1.0 mol%), PPh 2 Py (15.8 mg, 6.0 mol%), TFA (9.1 mg, 8.0 mol%) and a stirring bar was added. Then, allene 1a (1.0 mmol) and CD 3 OD (1.2 mmol) and toluene (2 ml) were injected by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 ml) of the 4560 series from Parr Instruments under argon atmosphere. At room temperature, the autoclave was flushed with CO three times, pressurized with CO to 40 bar. The reaction was performed for 20 h at 110 o C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released and isooctane (100 ul) (internal standard) was added to the solution. The yield and selectivity were measured by GC analysis. After removing the solvent by vacuum, the residue was directly purified by flash chromatography on silica gel (eluent: pentane/ethyl acetate = 100/1) and the result was analyzed according to the 1 H NMR spectra. (2) A vial (4 ml) was charged with Pd(OAc) 2 (2.2 mg, 1.0 mol%), PPh 2 Py (15.8 mg, 6.0 mol%), TFAd (9.2 mg, 8.0 mol%) and a stirring bar was added. Then, allene 1a (1.0 mmol) and MeOH (1.2 mmol) S6

8 and toluene (2 ml) were injected by syringe. The vial was placed in an alloy plate, which was transferred into an autoclave (300 ml) of the 4560 series from Parr Instruments under argon atmosphere. At room temperature, the autoclave was flushed with CO three times, pressurized with CO to 40 bar. The reaction was performed for 20 h at 110 o C. After the reaction finished, the autoclave was cooled to room temperature and the pressure was carefully released and isooctane (100 ul) (internal standard) was added to the solution. The yield and selectivity were measured by GC analysis. After removing the solvent by vacuum, the residue was directly purified by flash chromatography on silica gel (eluent: pentane/ethyl acetate = 100/1) and the result was analyzed according to the 1 H NMR spectra. 8. Kinetic progress procedure for 4a: A 25 ml autoclave was charged under argon atmosphere with Pd(OAc) 2 (1.0 mol%), PPh 2 Py (6.0 mol%), TFA (8.0 mol%). Then, allene 1a (4.0 mmol), n-butanol (4.8 mmol), dodecane (0.4 ml as internal) and toluene (8.0 ml) were injected by syringe. Then, the autoclave was pressurized with 40 bar CO at room temperature. The reaction was heated to 110 o C. Then sampling the reaction mixture from a special valve on autoclave with a specific time and analyzed by GC. 9. Detailed optimization for the synthesis of 3a: Table S1, ligand effect: S7

9 Table S2, acid co-catalyst effect: + nbuoh + CO 1 mol% Pd(OAc) 2, 2 mol% Xantphos 4 mol% Acid Toluene, 110 o C, 20 h OnBu + O OnBu 1a 2a 40 bar 3a 5a entry Acid 3a yield (%) 5a PTSA MSA TFA AcOH GC yield using isooctane as internal standard. Table S3, Pd catalyst effect: GC yield using isooctane as internal standard. Table S4, Pd catalyst effect: S8

10 GC yield using isooctane as internal standard. Table S5, temperature and pressure of CO effect: 10. Detailed optimization for the synthesis of 4a: Table S6, acid co-catalyst effect: S9

11 Table S7, optimizing of the amounts of acid co-catalyst and ligand: Table S8, Pd catalyst effect: Table S9, solvent effect: Table S10, temperature effect: S10

12 Characterization of products (E)-butyl 4-phenylbut-3-enoate: mg, 85% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 5H), 6.42 (dt, J = 15.9, 1.4 Hz, 1H), 6.23 (dt, J = 15.9, 7 Hz, 1H), 4.04 (t, J = 6.7 Hz, 2H), 3.17 (dd, J = 7.0, 1.3 Hz, 2H), (m, 2H), (m, 2H), 0.86 (t, J = 7.3 Hz, 3H). 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , 64.98, 38.76, 30.91, 19.40, (E)-butyl 4-(4-fluorophenyl)but-3-enoate: mg, 76% yield, light green liquid, 1 mmol scale substrate. S11

13 1 H NMR (300M, CDCl 3 ) δ (m, 2H), (m, 2H), 6.48 (dt, J = 15.9, 1.4 Hz, 1H), 6.26 (dt, J = 15.9, 7.0 Hz, 1H), 4.16 (t, J = 6.7 Hz, 2H), 3.26 (dd, J = 7.0, 1.4 Hz, 2H), (m, 2H), (m, 2H), 0.98 (t, J = 7.3 Hz, 3H). 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , , , , , , 64.85, 38.46, 30.81, 19.29, HRMS (EI) calculated for C 14 H 17 FO 2 : ; found: (E)-butyl 4-(4-chlorophenyl)but-3-enoate: mg, 79% yield, light green liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 4H), 6.44 (dt, J = 15.9, 1.3 Hz, 1H), 6.29 (dt, J = 15.9, 6.9 Hz, 1H), 4.13 (t, J = 6.7 Hz, 2H), 3.24 (dd, J = 6.9, 1.3 Hz, 2H), (m, 2H), (m, 2H), 0.95 (t, J = 7.4 Hz, 3H). 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , 64.95, 38.54, 30.83, 19.33, HRMS (ESI) calculated for (C 14 H 17 ClO 2 +H) + : ; found: (E)-butyl 4-(3-chlorophenyl)but-3-enoate mg, 70% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 1H), (m, 3H), (m, 1H), 6.36 (dt, J = 15.9, 6.6 Hz, 1H), 4.17 (t, J = 6.7 Hz, 2H), 3.28 (dd, J = 6.6, 1.0 Hz, 2H), (m, 2H), (m, 2H), 0.98 (t, J = 7.4 Hz, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , , , 64.95, 38.48, 30.82, 19.32, HRMS (ESI) calculated for (C 14 H ClO 2 +H) + : ; found: ; calculated (C 14 H ClO 2 +H) + : ; found: S12

14 (E)-butyl 4-(2-chlorophenyl)but-3-enoate mg, 76% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 1H), (m, 1H), (m, 2H), 6.93 (dt, J = 15.8, 1.5 Hz, 1H), 6.36 (dt, J = 15.8, 7.1 Hz, 1H), 4.18 (t, J = 6.7 Hz, 2H), 3.35 (dd, J = 7.2, 1.6 Hz, 2H), (m, 2H), (m, 2H), 0.99 (t, J = 7.4 Hz, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , , , 65.04, 38.78, 30.90, 19.40, HRMS (ESI) calculated for (C 14 H ClO 2 +H) + : ; found: ; calculated for (C 14 H ClO 2 +H) + : ; found: (E)-butyl 4-(4-bromophenyl)but-3-enoate mg, 81% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 2H), (m, 2H), 6.46 (d, J = 15.9, 1H), 6.34 (dt, J = 15.9, 6.7 Hz, 1H), 4.16 (t, J = 6.7 Hz, 2H), 3.27 (dd, J = 6.8, 1.1 Hz, 2H), (m, 2H), (m, 2H), 0.98 (t, J = 7.3 Hz, 3H). 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , , 64.79, 38.39, 30.67, 19.17, HRMS (EI) calculated for C 14 H 17 BrO 2 : ; found: ; calculated for C 14 H BrO 2 : ; found: (E)-butyl 4-(p-tolyl)but-3-enoate: mg, 68% yield, light green liquid, 1 mmol scale substrate. S13

15 1 H NMR (300M, CDCl 3 ) δ 7.29 (d, J = 8.1 Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H), 6.49 (dt, J = 15.8, 1.4 Hz, 1H), 6.27 (dt, J = 15.9, 7.0 Hz, 1H), 4.14 (t, J = 6.7 Hz, 2H), 3.25 (dd, J = 7.1, 1.4 Hz, 2H), 2.36 (s, 3H), (m, 2H), (m, 2H), 0.97 (t, J = 7.4 Hz, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , 64.91, 38.74, 30.89, 21.44, 21.41, 19.38, HRMS (ESI) calculated for (C 15 H 20 O 2 +H) + : ; found: (E,Z)-butyl 4-cyclohexylbut-3-enoate: mg, 61% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 2H), (m, 2H), (m, 2H), (m, 1H), (m,7h), (m, 7H), (m, 3H). 13 C NMR (75 MHz, CDCl 3 ) δ , (E), (Z), (E), (Z), 64.50, 40.78, 38.41, 33.11, 32.99, 32.98, 30.85, 26.34, 26.18, 26.01, 19.31, HRMS (EI) calculated for C 9 H 16 O 2 : ; found: O OBn (E,Z)-benzyl 4-cyclohexylbut-3-enoate: mg, 63% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 5H), (m, 2H), (m, 2H), (m, 2H), (m, 1H), (m, 5H), (m, 5H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , , , 66.47, 40.82, 38.39, 33.00, 26.38, HRMS (EI) calculated for C 9 H 16 O 2 : ; found: S14

16 (E,Z)-butyl pent-3-enoate: 2.37g, 76% yield, colorless liquid, 20 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 2H), (m, 2H), [ (m, 0.49H), (m, 1.30H) E, Z type], (m, 2H), (m, 3H), (m, 2H), 0.94 (t, J = 7.3 Hz, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ (E), (Z), (E), (Z), (E), (Z), 64.68(Z), 64.63(E), 38.31(E), 32.92(Z), 30.86, 19.33, 18.09(E), 13.90, 13.11(Z). HRMS (EI) calculated for C 9 H 16 O 2 : ; found: (E,Z)-diethyl pent-2-enedioate: mg, 65% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ 6.94 (dt, J = 15.7, 7.2 Hz, E type), 6.42 (dt, J = 11.5, 6.9 Hz, Z type), 5.86 (dt, J = 15.7, 1.7 Hz, 1H), (m, 4H), 3.69 (dd, J = 6.9, 2.0 Hz, E type), 3.16 (dd, J = 7.2, 1.6 Hz, Z type), (m, 6H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , , 61.18, 60.50, 37.51, 33.38, 14.29, HRMS (ESI) calculated for (C 9 H 14 O 4 +H) + : ; found: calculated for (C 9 H 14 O 4 +Na) + : ; found: butyl 4-methylpent-3-enoate: 96.8 mg, 57% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 1H), 4.06 (t, J = 6.7 Hz, 2H), (m, 2H), (m, 8H), (m, 2H), 0.92 (t, J = 7.4 Hz, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , 64.65, 34.11, 30.93, 25.89, 19.38, 18.20, HRMS (EI) calculated for C 10 H 18 O 2 : ; found: S15

17 (E)-methyl 4-phenylbut-3-enoate: mg, 80% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 5H), 6.40 (dt, J = 16.0, 1.3 Hz, 1H), 6.21 (dt, J = 15.9, 7.0 Hz, 1H), 3.62 (s, 3H), 3.16 (dd, J = 7.0, 1.4 Hz, 2H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , , 52.13, (E)-ethyl 4-phenylbut-3-enoate: mg, 73% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 5H), 6.55 (dt, J = 15.7, 1.3 Hz, 1H), 6.37 (dt, J = 15.9, 7.0 Hz, 1H), 4.23 (q, J = 7.1 Hz, 2H), 3.30 (dd, J = 7.0, 1.4 Hz, 2H), 1.34 (t, J = 7.1 Hz, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , 61.04, 38.74, (E)-benzyl 4-phenylbut-3-enoate: mg, 69% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 10H), 6.59 (dt, J = 15.9, 1.4 Hz, 1H), 6.41 (dt, J = 15.8, 7.0 Hz, 1H), 5.25 (s, 2H), 3.39 (dd, J = 6.9, 1.3 Hz, 2H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , , , , , 66.80, S16

18 (E)-phenethyl 4-phenylbut-3-enoate: mg, 71% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 10H), 6.57 (dt, J = 15.9, 1.4 Hz, 1H), 6.36 (dt, J = 15.9, 7.0 Hz, 1H), 4.44 (t, J = 7.0 Hz, 2H), 3.33 (dd, J = 7.1, 1.4 Hz, 2H), 3.05 (t, J = 7.0 Hz, 2H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , , , , , 65.43, 38.64, (E)-nonyl 4-phenylbut-3-enoate: mg, 76% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 5H), 6.56 (dt, J = 15.9, 1.3 Hz, 1H), 6.37 (dt, J = 15.9, 7.0 Hz, 1H), 4.17 (t, J = 6.8 Hz, 2H), 3.30 (dd, J = 7.0, 1.4 Hz, 2H), (m, 2H), (m, 12H), (m, 3H). 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , 65.24, 38.73, 32.11, 29.73, 29.50, 29.48, 28.85, 26.16, 22.92, (E)-cyclopropylmethyl 4-phenylbut-3-enoate: mg, 62% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 5H), 6.57 (dt, J = 15.9, 1.4 Hz, 1H), 6.39 (dt, J = 15.9, 6.9 Hz, 1H), 4.02 (d, J = 7.3 Hz, 2H), 3.34 (dd, J = 7.0, 1.3 Hz, 2H), (m, 1H), (m, 2H), (m, 2H) 13 C NMR (75 MHz, CDCl3) δ , , , , , , , , 69.73, 38.60, 9.99, HRMS (EI) calculated for C 14 H 16 O 2 : ; found: S17

19 (E)-isopropyl 4-phenylbut-3-enoate: mg, 61% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 5H), 6.55 (dt, J = 15.9, 1.3 Hz, 1H), 6.37 (dt, J = 15.9, 7.0 Hz, 1H), 5.11 (hept, J = 6.3 Hz, 1H), 3.27 (dd, J = 7.0, 1.4 Hz, 2H), 1.32 (d, J = 6.3 Hz, 6H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , 68.35, 39.00, (E)-cyclohexyl 4-phenylbut-3-enoate: mg, 62% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 5H), 6.56 (dt, J = 15.9, 1.3 Hz, 1H), 6.38 (dt, J = 15.9, 7.0 Hz, 1H), (m, 1H), 3.29 (dd, J = 7.0, 1.4 Hz, 2H), (m, 4H), (m, 6H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , 73.20, 39.00, 31.80, 25.57, (E)-bicyclo[2.2.1]heptan-2-yl 4-phenylbut-3-enoate: mg, 61% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (400M, CDCl 3 ) δ (m, 5H), 6.39 (dt, J = 15.9, 1.5 Hz, 1H), 6.20 (dt, J = 15.9, 7.1 Hz, 1H), 4.56 (dt, J = 7.1, 1.3 Hz, 1H), 3.10 (dd, J = 7.1, 1.5 Hz, 2H), (m, 2H), (m, 1H), (m, 4H), (m, 3H) 13 C NMR (101 MHz, CDCl 3 ) δ , , , , , , , 78.17, 41.65, 39.82, 38.95, 35.60, 35.50, 28.34, HRMS (EI) calculated for C 17 H 20 O 2 : ; found: S18

20 (E)-2-hydroxycyclohexyl 4-phenylbut-3-enoate: mg, 46% yield, slight green liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 5H), 6.55 (dt, J = 15.8, 1.4 Hz, 1H), 6.36 (dt, J = 15.9, 6.9 Hz, 1H), (m, 1H), (m, 1H), (m, 2H), 2.53 (br. s, 1H), (m, 2H), (m, 2H), (m, 4H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , 78.67, 72.76, 38.78, 33.24, 30.14, 24.03, HRMS (ESI) calculated for [C 16 H 20 O 3 +Na] + : ; found: (3E,3'E)-decane-1,10-diyl bis(4-phenylbut-3-enoate): mg, 70% yield, white solid, 0.5 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 10H), 6.56 (dt, J = 15.8, 1.3 Hz, 2H), 6.37 (dt, J = 15.9, 7.0 Hz, 2H), 4.17 (t, J = 6.7 Hz, 4H), 3.31 (dd, J = 7.0, 1.4 Hz, 4H), (m, 4H), (m, 14H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , 65.15, 38.68, 29.61, 29.41, 28.79, HRMS (ESI) calculated for [C 30 H 38 O 4 +Na] + : ; found: mg, 41% yield, oil liquid, 1 mmol scale substrate. S19

21 1 H NMR (300M, CDCl 3 ) δ (m, 10H), 6.50 (dt, J = 15.9, 1.4 Hz, 1H), 6.26 (dt, J = 15.9, 7.0 Hz, 1H), 5.74 (d, J = 8.3 Hz, 1H), 5.14 (s, 2H), (m, 1H), 4.49 (qd, J = 11.3, 3.9 Hz, 2H), 3.75 (s, 3H), 3.25 (dd, J = 7.1, 1.4 Hz, 2H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , , , , , , 67.37, 64.40, 53.49, 53.01, 52.98, HRMS (ESI) calculated for [C 22 H 23 NO 6 +H] + : ; found: ; [C 22 H 23 NO 6 +Na] + : ; found: mg, 44% yield, light green liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 5H), 6.54 (dt, J = 15.9, 1.5 Hz, 1H), 6.34 (dt, J = 15.9, 7.0 Hz, 1H), 5.59 (d, J = 5.0 Hz, 1H), 4.66 (dd, J = 7.9, 2.5 Hz, 1H), (m, 2H), (m, 2H), (m, 1H), 3.33 (dd, J = 6.9, 1.6 Hz, 2H), 1.50 (d, J = 2.5 Hz, 6H), 1.36 (d, J = 5.9 Hz, 6H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , , , 96.49, 71.26, 70.89, 70.62, 66.19, 63.95, 38.45, 26.15, 25.16, HRMS (ESI) calculated for [C 22 H 28 O 7 +H] + : ; found: ; [C 22 H 28 O 7 +Na] + : ; found: mg, 70% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 5H), 6.41 (dt, J = 15.9, 1.4 Hz, 1H), 6.22 (dt, J = 15.9, 7.0 Hz, 1H), (m, 1H), 3.14 (dd, J = 7.0, 1.4 Hz, 2H), (m, 1H), (m, 1H), (m, 2H), (m, 2H), (m, 2H), (m, 6H), (m, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , , 74.83, 47.27, 41.14, 39.00, 34.48, 31.63, 26.56, 23.73, 22.28, 21.00, HRMS (EI) calculated for C 20 H 28 O 2 : ; found: S20

22 H O O H Ph mg, 58% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 5H), 6.54 (dt, J = 15.9, 1.4 Hz, 1H), 6.35 (dt, J = 15.9, 7.0 Hz, 1H), (m, 1H), (m, 2H), 3.29 (dd, J = 7.0, 1.3 Hz, 2H), (m, 3H), (m, 2H), (m, 2H), 1.33 (s, 3H), 1.21 (d, J = 8.5 Hz, 1H), 0.89 (s, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , , , 63.27, 45.88, 40.94, 38.77, 38.24, 36.16, 31.88, 31.58, 26.52, HRMS (ESI) calculated for [C 21 H 26 O 2 +Na] + : ; found: mg, 64% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ (m, 5H), 6.57 (dt, J = 15.8, 1.4 Hz, 1H), 6.38 (dt, J = 15.9, 7.0 Hz, 1H), (m, 1H), 3.33 (dd, J = 7.0, 1.4 Hz, 2H), (m, 1H), (m, 1H), (m, 2H), (m, 2H), (m, 1H), 0.98 (s, 3H),0.95 (s, 3H),0.91 (s, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , 80.49, 49.07, 48.07, 45.13, 38.96, 37.02, 28.29, 27.35, 19.95, 19.09, HRMS (EI) calculated for C 20 H 26 O 2 : ; found: Ph O O H H mg, 67% yield, white solid, 1 mmol scale substrate. S21

23 1 H NMR (300M, CDCl 3 ) δ (m, 5H), 6.56 (dt, J = 15.9, 1.3 Hz, 1H), 6.39 (dt, J = 15.9, 6.9 Hz, 1H), (m, 1H), (m, 1H), 3.30 (dd, J = 7.0, 1.3 Hz, 2H), (m, 2H), (m, 5H), (m, 33H), 0.77 (s, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , , , , , 74.49, 56.85, 56.35, 50.19, 42.48, 39.92, 39.74, 38.89, 38.31, 37.18, 36.75, 36.41, 36.02, 32.09, 32.03, 28.46, 28.21, 27.97, 24.49, 24.09, 23.07, 22.82, 21.24, 19.52, 18.95, HRMS (EI) calculated for C 37 H 54 O 2 : ; found: (E)-methyl 2-methyl-3-phenylacrylate: mg, 67% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ 7.76 (q, J = 1.5 Hz, 1H), (m, 5H), 3.87 (s, 3H), 2.18 (d, J = 1.6 Hz, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , 52.19, HRMS (EI) calculated for C 11 H 12 O 2 : ; found: (E)-ethyl 2-methyl-3-phenylacrylate: mg, 53% yield, colorless liquid, calculate according 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ 7.60 (q, J = 1.5 Hz, 1H), (m, 5H), 4.18 (q, J = 7.1 Hz, 2H), 2.03 (d, J = 1.5 Hz, 3H), 1.26 (t, J = 7.1 Hz, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , 61.08, 14.56, HRMS (EI) calculated for C 12 H 14 O 2 : ; found: S22

24 (E)-butyl 2-methyl-3-phenylacrylate: mg, 72% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ 7.75 (q, J = 1.5 Hz, 1H), (m, 5H), 4.28 (t, J = 6.6 Hz, 2H), 2.18 (d, J = 1.5 Hz, 3H), (m, 2H), (m, 2H), (m, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , 65.03, 31.02, 19.53, 14.30, HRMS (EI) calculated for C 14 H 18 O 2 : ; found: (E)-nonyl 2-methyl-3-phenylacrylate: mg, 67% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ 7.75 (q, J = 1.5 Hz, 1H), (m, 5H), 4.27 (t, J = 6.7 Hz, 2H), 2.18 (d, J = 1.5 Hz, 3H), (m, 2H), (m, 12H), (m, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , 65.34, 32.11, 29.75, 29.54, 29.50, 28.95, 26.30, 22.93, 14.36, HRMS (EI) calculated for C 19 H 28 O 2 : ; found: O O (E)-benzyl 2-methyl-3-phenylacrylate: mg, 52% yield, colorless liquid, calculate according 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ 7.64 (t, J = 1.6 Hz, 1H), (m, 10H), 5.15 (s, 2H), 2.04 (d, J = 1.5 Hz, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , , , , 66.84, S23

25 HRMS (EI) calculated for C 17 H 16 O 2 : ; found: (E)- (1S,4S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl 2-methyl-3-phenylacrylate: mg, 47% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ 7.77 (q, J = 1.5 Hz, 1H), (m, 5H), (m, 1H), (m, 1H), 2.20 (d, J = 1.5 Hz, 3H), (m, 1H), (m, 2H), (m, 2H), (m, 1H), 1.02 (s, 3H), 0.97 (s, 6H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , 80.64, 49.23, 48.04, 45.19, 37.19, 28.33, 27.61, 19.98, 19.16, 14.34, HRMS (EI) calculated for C 20 H 26 O 2 : ; found: mg, 41% yield, white solid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ 7.59 (q, J = 1.4 Hz, 1H), (m, 5H), (m, 1H), (m, 1H), (m, 2H), 2.03 (d, J = 1.5 Hz, 3H), (m, 6H), (m, 18H), 0.97 (s, 3H), (m, 9H), 0.60 (s, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , , , 74.67, 56.92, 56.37, 50.26, 42.55, 39.98, 39.77, 38.48, 37.29, 36.88, 36.44, 36.07, 32.18, 32.11, 28.51, 28.27, 28.13, 24.55, 24.11, 23.11, 22.85, 21.30, 19.64, 18.98, 14.36, HRMS (ESI) calculated for C 37 H 54 NaO 2 + : ; found: S24

26 (E)-butyl 2-methyl-3-(p-tolyl)acrylate: mg, 54% yield (NMR yield), colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ 7.58 (s, 1H), 7.22 (d, J = 8.1 Hz, 2H), 7.11 (d, J = 8.3 Hz, 2H), 4.12 (t, J = 6.6 Hz, 2H), 2.28 (s, 3H), 2.03 (d, J = 1.5 Hz, 3H), (m, 2H), (m, 2H), 0.88 (t, J = 7.4 Hz, 2H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , , , 64.95, 31.04, 21.55, 19.54, 14.33, HRMS (EI) calculated for C 15 H 20 O 2 : ; found: (E)-butyl 3-cyclohexyl-2-methylacrylate: mg, 64% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ 6.50 (dq, J = 9.7, 1.5 Hz, 1H), 4.05 (t, J = 6.6 Hz, 2H), (m, 1H), 1.77 (d, J = 1.4 Hz, 3H), (m, 7H), (m, 2H), (m, 5H), 0.88 (t, J = 7.3 Hz, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , 64.59, 37.98, 32.18, 31.03, 26.15, 25.90, 19.53, 14.04, HRMS (EI) calculated for C 14 H 24 O 2 : ; found: diethyl 2-methylfumarate: 77.1 mg, 41% yield, colorless liquid, 1 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ 6.71 (q, J = 1.6 Hz, 1H), 4.17 (p, J = 7.2 Hz, 4H), 2.22 (d, J = 1.6 Hz, 3H), 1.25 (td, J = 7.1, 3.2 Hz, 6H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , 61.82, 60.86, 14.51, 14.44, HRMS (ESI) calculated for (C 9 H 14 O 4 +H) + : ; found: S25

27 (E)-butyl 2-methylbut-2-enoate: 1.21 g, 43% yield, colorless liquid, 18 mmol scale substrate. 1 H NMR (300M, CDCl 3 ) δ 6.85 (qq, J = 6.9, 1.4 Hz, 1H), 4.14 (t, J = 6.6 Hz, 2H), 1.84 (p, J = 1.2 Hz, 3H), 1.79 (dq, J = 7.1, 1.2 Hz, 3H), (m, 2H), (m, 2H), 0.95 (t, J = 7.4 Hz, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , 64.42, 30.98, 19.46, 14.46, 13.93, HRMS (ESI) calculated for (C 9 H 16 O 2 +H) + : ; found: (E)-(3-butoxyprop-1-en-1-yl)benzene: 1 H NMR (300M, CDCl 3 ) δ (m, 5H), 6.53 (dt, J = 15.9, 1.4 Hz, 1H), 6.22 (dt, J = 15.9, 6.0 Hz, 1H), 4.06 (dd, J = 6.0, 1.5 Hz, 2H), 3.41 (t, J = 6.6 Hz, 2H), (m, 2H), (m, 2H), 0.86 (t, J = 7.3 Hz, 3H) 13 C NMR (75 MHz, CDCl 3 ) δ , , , , , 71.68, 70.51, 32.16, 19.67, References 1. Hu, J.; Xie, Y.; Huang, H., Palladium-Catalyzed Insertion of an Allene into an Aminal: Aminomethylamination of Allenes by CappleN Bond Activation. Angewandte Chemie International Edition 2014, 53 (28), Brown, T. J.; Weber, D.; Gagné, M. R.; Widenhoefer, R. A., Mechanistic Analysis of Gold(I)- Catalyzed Intramolecular Allene Hydroalkoxylation Reveals an Off-Cycle Bis(gold) Vinyl Species and Reversible C O Bond Formation. Journal of the American Chemical Society 2012, 134 (22), Liu, Q.; Wu, L.; Jiao, H.; Fang, X.; Jackstell, R.; Beller, M., Domino Catalysis: Palladium- Catalyzed Carbonylation of Allylic Alcohols to β,γ-unsaturated Esters. Angewandte Chemie International Edition 2013, 52 (31), S26

28 NMR spectra of products S27

29 S28

30 S29

31 S30

32 S31

33 S32

34 S33

35 S34

36 OBn O O OBn S35

37 S36

38 O O EtO OEt O O EtO OEt S37

39 S38

40 S39

41 S40

42 S41

43 S42

44 S43

45 S44

46 S45

47 S46

48 S47

49 S48

50 S49

51 S50

52 S51

53 S52

54 O O H H Ph O O H H Ph S53

55 S54

56 S55

57 S56

58 S57

59 S58

60 S59

61 O O O O S60

62 S61

63 S62

64 S63

65 S64

66 S65

67 S66

68 S67

69 Ph D OCD 3 + Ph O H 3aa' 3aa'' yield 76% 3aa':3aa'' = 68:32 O OCD 3 S68

70 S69