Supporting Information for

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1 Supporting Information for Regioselective Cis Insertion of DMAD into Au-P Bonds: Effect of Auxiliary Ligands on Reaction Mechanism Hitoshi Kuniyasu, * Takuya Nakajima, Takashi Tamaki, Takanori Iwasaki, and Nobuaki Kambe * Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka , Japan Table of Contents General Comments S2 1. The Reaction of Au(SPh)(PPh 3 ) (1a) with Dimethyl Acetylendicarboxylate (2, DMAD) 1-1. General Procedure S Preparation of Authentic Z-3a S The Photo-irradiated Isomerization of Z-3a to E-3a S The Photo-irradiated Isomerization of the Solution of Z-3a in the Presence of Z- Au(SPh)[C(CO 2 Et)=C(CO 2 Et)(PPh 3 )] 1-5. Determination of Reaction Orders of the Reaction of Au(SPh)(PPh 3 ) (1a) with Dimethyl Acetylendicarboxylate (2, DMAD) S4 S Electronic Effect in Ar of Au(SAr)(PPh 3 ) (1) S5 2. The Reaction of Au(Cl)(PPh 3 ) 2 (5) with Dimethyl Acetylendicarboxylate (2, DMAD) S6 3. NMR Spectra S8 4. X-ray Crystallography Information 4-1. X-ray Crystallographic Analysis of 3a S X-ray Crystallographic Analysis of 6 S13 S1

2 General Comments. The 31 P and 1 H NMR spectra in benzene-d 6 and CD 2 Cl 2 were measured with a JEOL JNM ECS400 (160 and 400 MHz, respectively) spectrometer. The chemical shifts of the 31 P NMR spectra were recorded relative to 85% H 3 PO 4 (aq) as an external standard, and S=P(C 6 H 4 OMe-p) 3 was used as an internal standard to calculate the yields of products. (The sensitivities of aurous complexes to the internal standard were measured individually.) 1. The Reaction of Au(SPh)(PPh 3 ) (1a) with Dimethyl Acetylendicarboxylate (2, DMAD) (eq 1): 1-1. General Procedure. Into a Pyrex NMR tube were added Au(SPh)(PPh 3 ) (1a, 11.9 mg, mmol), S=P(C 6 H 4 OMe-p) 3 (3.8 mg, mmol) and C 6 D 6 (0.6 ml) in a glove box. After measuring the sensitivity of 1a to S=P(C 6 H 4 OMe-p) 3 by 31 P NMR spectroscopy, dimethyl acetylenedicarboxylate (2, DMAD, 4.1 mg, mmol) was added into the NMR tube. Then the reaction at room temperature was monitored by 31 P and 1 H NMR spectroscopies. A new signal of Z-3a appeared at δ 20.1 (singlet) by 31 P NMR spectrum in 44% yield after 20 min. The 1 H NMR spectrum showed generation of a couple of singlet at δ 3.07 and The yield of 3a reached 94% after 3 h Preparation of Authentic Z-3a. Into a two-necked reaction vessel equipped with a stirring bar were added 1a (107.6 mg, 0.19 mmol), benzene (0.5 ml), and 2 (29.7 mg, mmol) under N 2 atmosphere. After stirring the orange solution for 4 h at room temperature, a yellow solid precipitated. The reaction mixture was transferred into a 100 ml eggplant flask, and the solvent was evaporated under reduced pressure. The solid was recrystallised from CH 2 Cl 2 /pentane to give mg (85%) of Z-3a as a yellow needle-shaped solid. A good crystal of Z-3a suitable for X-ray diffraction analysis was recrystallized from CH 2 Cl 2 /pentane solution and the crystallographic data was attached at the end of this Supporting Information. Z-3a: yellow solid. mp: 142 C (dec). 1 H NMR (400 MHz, CD 2 Cl 2 ): δ 3.43 (s, 3 H), 3.81 (s, 3 H), 6.80 (d, J = 7.6 Hz, 3 H), 6.96 (d, J = 6.4 Hz, 2 H), (m, 6 H), (m, 9 H). 13 C NMR (100 MHz, CD 2 Cl 2 ): δ 52.1 (s), 52.6 (s), (d, J = Hz), (d, J = 91.0 Hz), (s), (s), (d, J =12.9 Hz), (s), (d, J = 2.9 Hz), (d, J = 9.1 Hz), (s), (d, J = 25.4 Hz), (d, J = 34.5 Hz), (d, J = 27.2 Hz). 31 P NMR (160 MHz, CD 2 Cl 2 ): δ 20.3 (s). IR (KBr) 3441, 3056, 2949, 1720, 1692, 1577, 1512, 1482, 1472, 1435, 1232, 1101, 1084, S2

3 1070, 1023, 1000, 892, 843, 776, 743, 722, 691, 605, 537, 517, 482, 459, 420 cm -1. Anal. Calcd for C 30 H 26 AuO 4 PS: C, 50.71; H, 3.69; S, Found: C, 50.75; H, 3.98; S, The Photo-irradiated Isomerization of Z-3a to E-3a (ref 8). Into a Pyrex NMR tube were added Z-3a (7.3 mg, 0.01 mmol), S=P(C 6 H 4 OMe-p) 3 (3.8 mg, 0.01 mmol) and CD 2 Cl 2 (0.5 ml). Then the solution was photo-irradiated by 500 W tungsten lamp with the sample cooled by ice bath, and the reaction was monitored by 31 P and 1 H NMR spectroscopies (Figure S1, 2). The generation of new singlet at δ 19.7 suspected as E-isomer of 3a was confirmed, and the ratios of E/Z were as follows: 1 h, 72/28; 2 h, 53/47; 4 h, 46/54. Then the sample was left under dark at room temperature. However, no E/Z ratio change was observed even after 14 h. Figure S1. A 31 P NMR spectrum of Z-3a. S3

4 Figure S2. A 31 P NMR spectrum of Z-3a after photo-irradiation for 4 h The Photo-irradiated Isomerization of the Solution of Z-3a in the Presence of Z- Au(SPh)[C(CO 2 Et)=C(CO 2 Et)(PPh 3 )] (eq S1). Into a Pyrex NMR tube were added Z-3a (7.3 mg, 0.01 mmol), Z-Au(SPh)[C(CO 2 Et)=C(CO 2 Et)(PPh 3 )] (7.4 mg, 0.01 mmol), S=P(C 6 H 4 OMe-p) 3 (3.8 mg, 0.01 mmol) and CD 2 Cl 2 (0.5 ml). Then the solution was photo-irradiated by 500 W tungsten lamp with the sample cooled by ice bath, and the reaction was monitored by 31 P and 1 H NMR spectroscopies (Figure S3, 4). Only two signals appeared at δ 19.7 (s) and 19.9 (s), ruling out the formation dimeric complex, which should show three signals. MeO 2 C CO 2 Me PhSAu PPh 3 Z-3a 0.01 mmol + hν CD 2 Cl 2, 0 C, 4 h isomerization MeO 2 C PhSAu E-3a PPh 3 CO 2 Me + EtO 2 C PhSAu PPh 3 CO 2 Et (S1) EtO 2 C PhSAu CO 2 Et PPh mmol dimerization Ph 3 P MeO 2 C PhSAu MeO 2 C AuSPh CO 2 Me PPh 3 CO 2 Me + Ph 3 P MeO 2 C PhSAu EtO 2 C AuSPh CO 2 Me PPh 3 CO 2 Et + Ph 3 P EtO 2 C PhSAu AuSPh CO 2 Et PPh 3 CO 2 Et S4

5 Figure S3. A 31 P NMR spectrum of a mixture of Z-3a and Z-Au(SPh)[C(CO 2 Et)=C(CO 2 Et)(PPh 3 )] before the photo-irradiation. Figure S4. A 31 P NMR spectrum of a mixture of Z-3a and Z-Au(SPh)[C(CO 2 Et)=C(CO 2 Et)(PPh 3 )] after photo-irradiation for 4 h Determination of Reaction Orders of the Reaction of Au(SPh)(PPh 3 ) (1a) with Dimethyl Acetylendicarboxylate (2, DMAD). Into a Pyrex NMR tube were added 1a (11.4 mg, 0.02 mmol), S5

6 S=P(C 6 H 4 OMe-p) 3 (1.9 mg, mmol) and CD 2 Cl 2 (0.7 ml) in a glove box. After measuring the sensitivity of 1a to S=P(C 6 H 4 OMe-p) 3 by 31 P NMR spectroscopy, the NMR tube was cooled by dry ice and 2 (0.40 mmol) was added. Then the reaction at -10 C was monitored by 31 P spectroscopy. Similarly, the reaction of 1a (56.8 mg, 0.10 mmol) with 2 (0.01 mmol) at 10 C was monitored by 1 H spectroscopy Electronic Effect in Ar of Au(SAr)(PPh 3 ) (1) (Table 2). Into a Pyrex NMR tube were added Au(SPh)(PPh 3 ) (1a, 11.4 mg, 0.02 mmol), S=P(C 6 H 4 OMe-p) 3 (1.9 mg, mmol) and CD 2 Cl 2 (0.7 ml) in a glove box. After measuring the sensitivity of 1a to S=P(C 6 H 4 OMe-p) 3 by 31 P NMR spectroscopy, 2 (0.40 mmol) was added into the NMR tube. Then the reaction at 0 C was monitored by 31 P and 1 H NMR spectroscopies. The formation of the corresponding adduct Z-3a was confirmed in 28% yield. Similarly, the corresponding insertion product Z-3b (Ar = C 6 H 4 Br-p) was detected in 16% under a similar reaction condition. However, no reaction took place when using 1g (Ar = C 6 H 4 NO 2 -p) even at 25 C for 12 h. 3b: 31 P NMR(160 MHz, CD 2 Cl 2 ): δ 20.3; Z-3c: 31 P NMR(160 MHz, CD 2 Cl 2 ): δ 20.3 ; Z-3d: 31 P NMR(160 MHz, CD 2 Cl 2 ): δ 20.3; 3e: 31 P NMR(160 MHz, CD 2 Cl 2 ): δ 18.9; Z-3f: 31 P NMR(160 MHz, CD 2 Cl 2 ): δ 20.2; Z-3h: 31 P NMR(160 MHz, toluene-d 8 ): δ 19.9; Z-3i: 31 P NMR(160 MHz, toluene-d 8 ): δ The Reaction of Au(Cl)(PPh 3 ) 2 (5) with Dimethyl Acetylendicarboxylate (2, DMAD) (eq 4). Into a Pyrex NMR tube were added Au(Cl)(PPh 3 ) 2 (5, 15.4 mg, 0.02 mmol), S=P(C 6 H 4 OMe-p) 3 (3.8 mg, mmol) and C 6 D 6 (0.75 ml) in a glove box. After measuring the sensitivity of 5 to S=P(C 6 H 4 OMep) 3 by 31 P NMR spectroscopy, dimethyl acetylenedicarboxylate (2, DMAD, 5.7 mg, 0.04 mmol) was added into the NMR tube. Then the reaction at room temperature was monitored by 31 P and 1 H NMR spectroscopies (Figure S5, 6). A new signal of 6 appeared at δ 20.8 by 31 P NMR spectrum. Other signals, which can be detected by the reaction of free PPh 3 with 2 (Figure S7) were also confirmed. For the products produced by the reaction of free PPh 3 with 2, see ref 10(a)-10(e) for details. 6: white solid. mp: 160 C (dec). 1 H NMR (400 MHz, CD 2 Cl 2 ): δ 3.43 (s, 3 H), 3.78 (s, 3 H), (m, 6 H), (m, 9 H). 13 C NMR (100MHz, CD 2 Cl 2 ): δ 52.2 (s), 52.7 (s), (d, J = Hz), (d, J = 91.5 Hz), (d, J = 12.5 Hz), (d, J = 9.6 Hz), (d, J = 3.0 Hz), (d, J = 23.9 Hz), (d, J = 32.7 Hz), (d, J = 23.9 Hz). 31 P NMR (160 MHz, CD 2 Cl 2 ): δ 21.2 (s). Anal. Calcd for C 24 H 21 AuClO 4 P: C, 45.27; H, 3.32; Found: C, 44.94; H, S6

7 Figure S5. A 31 P NMR spectrum of 5 in C 6 D 6. Figure S6. A 31 P NMR spectrum of the reaction of 5 with 2 in C 6 D 6. S7

8 Figure S7. A 31 P NMR spectrum of the reaction solution of free PPh 3 with 2 in C 6 D NMR Spectra Figure S8. A 1 H NMR spectrum of Z-3a in CD 2 Cl 2. S8

9 Figure S9. A 13 C NMR spectrum of Z-3a in CD 2 Cl 2. Figure S10. A 31 P NMR spectrum of Z-3a in CD 2 Cl 2. S9

10 Figure S11. A 1 H NMR spectrum of 6 in CD 2 Cl 2. Figure S12. A 13 C NMR spectrum of 6 in CD 2 Cl 2. S10

11 Figure S13. A 31 P NMR spectrum of 6 in CD 2 Cl X-ray Crystallography Information 4-1. X-ray Crystallographic Analysis of 3a Single crystals of 3a suitable for X-ray crystallography were obtained by recrystallization from CH 2 Cl 2 /pentane. The crystal was mounted on the CryoLoop (Hampton Research Corp.) with a layer of light mineral oil and placed in a nitrogen stream at 123(2) K. Measurements were made on a Rigaku RAXIS-RAPID Imaging Plate diffractometer (Mo-Kα). The structure of 3a was solved by direct methods (SIR2004 ref#1 ). The structure was refined on F 2 by full-matrix least-squares method using SHELXL- 97. Non-hydrogen atoms were anisotropically refined. Hydrogen atoms were included in the refinement on calculated positions riding on their carrier atoms. The function minimized was [Σw(F 2 o F 2 c ) 2 ] (w = 1 / [σ 2 (F 2 o ) + (ap) 2 +bp]), where P = (Max(F 2 o,0)+2 F 2 c ) / 3 with σ 2 (F 2 o ) for counting statistics. The function R1 and wr2 were (Σ F o F 2 c /Σ F o ) and [Σ(w(F 2 o F 2 c ) 2 ) / Σw(F 2 o ) 2 )] 1/2, respectively. The large residual electron density is located near the Au atom. S11

12 Figure S14. Molecular structure of 3a with 50% thermal ellipsoids. All hydrogen atoms are omitted for clarity. Selected bond distances (Å): Au1 S (4); Au1 C1 2.01(2); C1 C2 1.34(2); C2 P1 1.81(1); C13 P1 1.82(1). Selected angles ( ): S1 Au1 C (4); Au1 C1 C2 132(1); Au1 C1 C (9); C2 C1 C3 116(1); P1 C2 C1 117(1); P1 C2 C5 118(1); C1 C2 C5 123(1); C2 P1 C (6). Table S1. Crystal Data and Data Collection Parameters of 3a. empirical formula C 30 H 26 AuO 4 PS formula weight color, description yellow, needle temperature, K 123(2) crystal system Monoclinic space group P2 1 (#4) a, Å (5) b, Å (1) c, Å (7) β, (2) S12

13 V, Å (2) Z 2 Dcalcd, g/cm θ max, deg 55.0 limiting indices 10 h 9, 21 k 21, 13 l 13 absorption coefficient, max. and min (max)/0.049 (min) F(000) crystal size, mm goodness-of-fit on F no. of reflections measured unique data (R int ) 6249 (0.1551) R1, wr2 [I > 2σ(I)] , R1, wr2 (all data) , Residual electron density, e Å (max), 5.87 (min) 4-2. X-ray Crystallographic Analysis of 6 Single crystals of 6 suitable for X-ray crystallography were obtained by recrystallization from CH 2 Cl 2 /pentane. The crystal was mounted on the CryoLoop (Hampton Research Corp.) with a layer of light mineral oil and placed in a nitrogen stream at 123(2) K. Measurements were made on a Rigaku RAXIS-RAPID Imaging Plate diffractometer (Mo-Kα). The structure of 6 was solved by direct methods (SHELX97 ref#2 ). The structure was refined on F 2 by full-matrix least-squares method using SHELXL- 97. Non-hydrogen atoms were anisotropically refined. Hydrogen atoms were included in the refinement on calculated positions riding on their carrier atoms. The function minimized was [Σw(F 2 o F 2 c ) 2 ] (w = 1 / [σ 2 (F 2 o ) + (ap) 2 +bp]), where P = (Max(F 2 o,0)+2 F 2 c ) / 3 with σ 2 (F 2 o ) for counting statistics. The function R1 and wr2 were (Σ F o F c /Σ F o ) and [Σ(w(F 2 o F 2 c ) 2 ) / Σw(F 2 o ) 2 ] 1/2, respectively. The large residual electron density is located near the Au atom. S13

14 Figure S15. Molecular structure of 6 with 50% thermal ellipsoids. All hydrogen atoms are omitted for clarity. Selected bond distances (Å): Au1 Cl (4); Au1 C1 1.95(1); C1 C2 1.38(2); C2 P1 1.79(2); C7 P1 1.81(1). Selected angles ( ): Cl1 Au1 C (4); Au1 C1 C2 135(1); Au1 C1 C (9); C2 C1 C3 114(1); P1 C2 C (9); P1 C2 C5 122(1); C1 C2 C5 123(1); C2 P1 C (6). Table S2. Crystal Data and Data Collection Parameters of 6. empirical formula C 24 H 21 AuClO 4 P formula weight color, description colorless, prism temperature, K 273 crystal system monoclinic space group P2 1 /n (#14) a, Å (11) b, Å (4) c, Å (14) S14

15 β, (3) V, Å (3) Z 4 Dcalcd, g/cm θ max, deg 54.9 limiting indices 20 h 16, 10 k 10, 25 l 25 absorption coefficient, max. and min (max)/0.216 (min) F(000) crystal size, mm goodness-of-fit on F no. of reflections measured unique data (R int ) 5233 (0.0710) R1, wr2 [I > 2σ(I)] R1, wr2 (all data) , Residual electron density, e Å (max), 3.92 (min) 1 M.C. Burla, R. Caliandro, M. Camalli, B. Carrozzini, G.L. Cascarano, L. De Caro, C. Giacovazzo, G. Polidori, D. Siliqi, R. Spagna (2007) 2 SHELX97: Sheldrick, G.M. (2008). Acta Cryst. A64, AUTHOR INFORMATION Corresponding Authors * kuni@chem.eng.osaka-u.ac.jp; kambe@chem.eng.osaka-u.ac.jp S15