Supporting Information for: Nickel-Catalyzed [4+2] Cycloaddition of Enones with Alkynes. Ichiro Koyama, Takuya Kurahashi,* and Seijiro Matsubara*

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1 Supporting Information for: Nickel-Catalyzed [4+2] Cycloaddition of Enones with Alkynes Ichiro Koyama, Takuya Kurahashi,* and Seijiro Matsubara* Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto-daigaku Katsura, Nishikyo-ku, Kyoto , Japan Contents Instrumentation and Chemicals S2 Experimental Procedure and Characterization Data for Products S3 RTEP Drawing of 3ah, 3ai, 4a S10 1 H NMR and 13 C NMR Spectra of Products S14 S1

2 Instrumentation and Chemicals All manipulations of oxygen- and moisture-sensitive materials were conducted in a dry box or with a standard Schlenk technique under a purified argon atmosphere. Nuclear magnetic resonance spectra were taken on Varian UNITY INVA 500 ( 1 H, 500 M Hz; 13 C, M Hz) spectrometer using tetramethylsilane ( 1 H) as an internal standard. 1 H NMR data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, quint = quintet, sext = sextet, sept = septet, br = broad, m = multiplet), coupling constants ( Hz), integration, and identification. 19 F NMR spectra were measured on a Varian rcury 200 ( 19 F, 188 M Hz) spectrometer with trifluoroacetic acid as an internal standard (δ = 0 ppm). X-Ray data were taken on a Bruker Smart APEX X-Ray diffracto- meter equipped with a large area CCD detector and Rigaku rcury CCD apparatus. GC-MS analyses and High-resolution mass spectra were obtained with a JEL JMS-700 spectrometer by electron ionization at 70 ev. Preparative recycling gel permeation chromatography (GPC) was performed with JAI LC-908 equipped with JAIGEL-1H and -2H columns (toluene as an eluent). Elemental analyses were carried out with a YANAK MT2 CHN CRDER machine at Kyoto University Elemental Analysis Center. Infrared spectra (IR) spectra were determined on a SHIMADZU FTIR-8200PC spectrometer. lting points were determined using a YANAK MP-500D. TLC analyses were performed by means of rck Kieselgel 60 F 254 (0.25 mm) Plates. Visualization was accomplished with UV light (254 nm) and/or an aqueous alkaline KMn 4 solution followed by heating. Flash column chromatography was carried out using Kanto Chemical silica gel (spherical, µm). Recrystallization was performed with a TECHN SIGMA Soltra mini. Unless otherwise noted, commercially available reagents were used without purification. Toluene was purchased from Wako Pure Chemical Co. stored over slices of sodium. Bis(1,5-cyclooctadiene)nickel and trimethylphosphine were purchased from Strem Chemicals, Inc. Enones were readily prepared by condensation of keto-ester and aldehyde. All reactions were performed in WHEATN 5.0 ml V-vial with screw cap. S2

3 Experimental Procedure for the Nickel-catalyzed Addition. General procedure. The reaction was performed in a 5 ml sealed vessel equipped with a Teflon-coated magnetic stirrer tip. An enone (0.5 mmol) and an alkyne (1.25 mmol) were added to a solution of Bis(1,5-dicyclooctadiene)nickel (14 mg, 0.05 mmol) and trimethylphosphine (15 mg, 0.20 mmol) in toluene (5 ml) in a dry box. The VIAL was taken outside the dry box and heated at 130 C for the indicated time. The resulting reaction mixture was cooled to ambient temperature and filtered through a silica gel pad, concentrated in vacuo. The residue was purified by flash silica gel column chromatography (30 g, 2x25 cm, hexane/ethyl acetate = 20:1) to give the corresponding 4H-pyrane derivatives. Ethyl 2-methyl-4-phenyl-5,6-dipropyl-4H-pyran-3-carboxylate (3aa). Pr Pr C 2 Et Yield: 99%, colorless oil. TLC: R f 0.57 (hexane/ethyl acetate = 4:1). 1 H NMR (CDCl 3 ) δ 7.23 (m, 4H; H), 7.15 (m, 1H; H), 4.17 (s, 1H; CH), 4.03 (q, J = 7.0 Hz, 2H; CH 2 ), 2.31 (s, 3H; CH 3 ), 2.19 (m, 2H; CH 2 ), 1.90 (m, 1H; CH 2 ), 1.71 (m, 1H; CH 2 ), 1.57 (m, 2H; CH 2 ), 1.44 (m, 1H; CH 2 ), 1.24 (m, 1H; CH 2 ), 1.17 (t, J = 7.0 Hz, 3H; CH 3 ), 0.94 (m, 3H; CH 3 ), 0.84 (m, 3H; CH 3 ). 13 C NMR (CDCl 3 ) δ (C), (C), (C), (C), (CH), (CH), (CH), (C), (C), 59.8 (CH 2 ), 41.4 (CH), 31.2 (CH 2 ), 31.0 (CH 2 ), 21.0 (CH 2 ), 20.7 (CH 2 ), 19.2 (CH 3 ), 14.1 (CH 3 ), 14.0 (CH 3 ), 13.7 (CH 3 ). IR (KBr): 2960, 1713, 1634, 1194, 1151, 1120, 1069, 699 cm 1. MS m/z (%): 328/329/330 (20/4/1) [M + ], 299/300/301 (16/4/1) [M + Et], 251 (100), 77 (2). HRMS Calcd for C 21 H 28 3 : M +, Found: m/z Ethyl 2-methyl-4,5,6-tripropyl-4H-pyran-3-carboxylate (3ea). Pr Pr Pr C 2 Et Yield: 99%, yellow oil. TLC: R f 0.82 (hexane/ethyl acetate = 9:1). 1 H NMR (CDCl 3 ) δ 4.18 (q, J = 7.0 Hz, 2H; CH 2 ), 3.17 (t, J = 4. 5 Hz, 1H; CH), 2.24 (s, 3H; CH 3 ), 2.12 (m, 2H; CH 2 ), 2.02 (m, 1H; CH 2 ), 1.93 (m, 1H; CH 2 ), 1.50 (m, 2H; CH 2 ), (m, 6H; CH 2, CH 2, CH 2 ), (m, 9H; CH 3, CH 3, CH 3 ), 0.84 (t, J = 7.0 Hz, 3H; CH 3 ). 13 C NMR (CDCl 3 ) δ (C), (C), (C), (C), (C), 59.7 (CH 2 ), 36.8 (CH), 34.1 (CH 2 ), 31.2 (CH 2 ), 31.0 (CH 2 ), 21.7 (CH 2 ), 20.7 (CH 2 ), 19.2 (CH 2 ), 17.9 (CH 3 ), 14.4 (CH 3 ), 14.3 (CH 3 ), 14.1 (CH 3 ), 13.7 (CH 3 ). IR (KBr): 2959, 2932, 2872, 1699, 1632, 1458, 1380, 1246, 1196, 1153, 1129, 1066 cm 1. MS m/z (%): 294 (1) [M + ], 251 (100) [M + Et]. HRMS Calcd for C 18 H 30 3 : M +, Found: m/z S3

4 Ethyl 2,4-diphenyl-5,6-dipropyl-4H-pyran-3-carboxylate (3fa) Pr Pr C 2 Et Yield: 82%, colorless oil. TLC: R f 0.40 (hexane/ethyl acetate = 4:1). 1 H NMR (CDCl 3 ) δ (m, 7H; H), (m, 2H; H), (m, 1H; H), 4.28 (s, 1H; CH), 3.85 (q, J = 7.0 Hz, 2H; CH 2 ), 2.28 (m, 2H; CH 2 ), 1.98 (m, 1H; CH 2 ), 1.81 (m, 1H; CH 2 ), 1.63 (qt, J = 7.0, 7. 5 Hz, 2H; CH 2 ), 1.49 (m, 1H; CH 2 ), 1.30 (m, 1H; CH 2 ), 0.96 (t, J = 7. 5 Hz, 3H; CH 3 ), 0.88 (m, 3H; CH 3 ), 0.85 (m, 3H; CH 3 ). 13 C NMR (CDCl 3 ) δ (C), (C), (C), (C), (C), (CH), (CH), (CH), (CH), (CH), (CH), (C), (C), 59.9 (CH 2 ), 42.1 (CH), 31.4 (CH 2 ), 21.1 (CH 2 ), 20.7 (CH 2 ), 14.1 (CH 3 ), 13.7 (CH 3 ), 13.5 (CH 3 ). IR (KBr): 2960, 1699, 1635, 1193, 1095, 697 cm 1. MS m/z (%): 390/391/392 (73/21/5) [M + ], 361/362/363 (27/7/2) [M + Et], 313 (100), 77 (1). HRMS Calcd for C 26 H 30 3 : M +, Found: m/z Ethyl 2-phenyl-4,5,6-tripropyl-4H-pyran-3-carboxylate (3ga). Pr Pr Pr C 2 Et Yield: 50%, yellow oil. TLC: R f 0.50 (hexane/ethyl acetate = 9:1). 1 H NMR (CDCl 3 ) δ (m, 5H; H), 3.95 (q, J = 7.0 Hz, 2H; CH 2 ), 3.24 (t, J = 4. 5 Hz, 1H; CH), 2.23 (m, 2H; CH 2 ), 2.09 (m, 1H; CH 2 ), 2.00 (m, 1H; CH 2 ), (m, 8H; CH 2, CH 2, CH 2, CH 2, CH 2 ), (m, 9H; CH 3, CH 3, CH 3 ), 0.91 (t, J = 7.0 Hz, 3H; CH 3 ). 13 C NMR (CDCl 3 ) δ (C), (C), (C), (C), (CH), (CH), (CH), (C), (C), 59.8 (CH 2 ), 36.9 (CH), 35.1 (CH 2 ), 31.4 (CH 2 ), 31.1 (CH 2 ), 21.8 (CH 2 ), 20.7 (CH 2 ), 18.0 (CH 2 ), 14.5 (CH 3 ), 14.2 (CH 3 ), 13.7 (CH 3 ), 13.6 (CH 3 ). IR (KBr): 2932, 2872, 1696, 1635, 1447, 1373, 1247, 1195, 1157, 1082, 765, 696 cm 1. MS m/z (%): 356 (1) [M + ], 313 (100) [M + Et], 77 (11). HRMS Calcd for C 23 H 32 3 : M +, Found: m/z Ethyl 2-methyl-4,5,6-triphenyl-4H-pyran-3-carboxylate (3ab). Yield: 74%, pale yellow oil. TLC: R f 0.34 (hexane/ethyl acetate = 4:1). 1 H NMR (CDCl 3 ) δ (m, 2H; H), (m, 4H; H), (m, 4H; H), (m, 3H; H), (m, 2H; H), 4.59 (s, 1H; CH), 4.14 (q, J = 7.0 Hz, 2H; CH 2 ), 2.51 (s, 3H; CH 3 ), 1.24 (t, J = 7.0 Hz, 3H; CH 3 ). 13 C NMR (CDCl 3 ) δ (C), (C), (C), (C), (C), (C), (CH), (CH), (CH), (CH), (CH), (CH), (CH), (CH), (CH), (C), (C), 60.1 (CH 2 ), 44.6 (CH), 19.2 (CH 3 ), 14.2 (CH 3 ). IR (KBr): 2967, 1714, 1635, 1454, 105, 1094, 699 cm 1. MS m/z (%): 296/297/298 (75/22/2) [M + ], 367/368/369 (24/6/1) [M + Et], 319 (100), 77 (10). HRMS Calcd for C 27 H 24 3 : M +, Found: m/z C 2 Et S4

5 Ethyl 5,6-bis(methoxymethyl)-2-methyl-4-phenyl-4H-pyran-3-carboxylate (3ac). Yield: 82%, colorless oil. TLC: R f 0.32 (hexane/ethyl acetate = 4:1). NMR (CDCl 3 ) δ (m, 4H; H), (m, 1H; H), 4.46 (s, 1H; CH), 4.15 (d, J = 1 3 Hz, 1H; CH 2 ), 4.04 (d, J = 1 3 Hz, 1H; CH 2 ), 4.03 (q, J = 7.0 Hz, 2H; CH 2 ), 3.93 (d, J = 1 2 Hz, 1H; CH 2 ), 3.68 (d, J = 1 2 Hz, 1H; CH 2 ), 3.37 (s, 3H; CH 3 ), 3.26 (s, 3H; CH 3 ), 2.39 (s, 3H; CH 3 ), 1.14 (t, J = 7.0 Hz, 3H; CH 3 ). C 2 Et 13 C NMR (CDCl 3 ) δ (C), (C), (C), (C), (CH), (CH), (CH), (C), (C), 68.0 (CH 2 ), 67.7 (CH 2 ), 59.9 (CH 2 ), 58.1 (CH 3 ), 57.7 (CH 3 ), 39.6 (CH), 18.9 (CH 3 ), 14.0 (CH 3 ). IR (KBr): 2920, 1713, 1635, 1454, 1200, 1093, 701 cm 1. MS m/z (%): 332/331 (9/2) [M + ], 287/288/289 (27/5/1) [M + Et], 255 (100), 77 (2). Anal. Calcd for C 19 H 24 5 : C, 68.66; H, 7.28;, Found: C, 68.61; H, 7.32;, H Ethyl 5-(2-methoxyethyl)-2-methyl-4-phenyl-6-propyl-4H-pyran-3-carboxylate (3ad). Pr C 2 Et Yield: 37%, colorless oil. TLC: R f 0.50 (hexane/ethyl acetate = 4:1). 1 H NMR (CDCl 3 ) δ (m, 4H; H), 7.16 (m, 1H; H), 4.17 (s, 1H; CH), 4.04 (q, J = 7.0 Hz, 2H; CH 2 ), 3.27 (m, 1H; CH 2 ), 3.24 (s, 3H; CH 3 ), 3.17 (m, 1H; CH 2 ), 2.31 (s, 3H; CH 3 ), 2.21 (m, 3H; CH 2,CH 2 ), 2.06 (m, 1H; CH 2 ), 1.59 (m, 2H; CH 2 ), 1.16 (t, J = 7.0 Hz, 3H; CH 3 ), 0.94 (m, 3H; CH 3 ). 13 C NMR (CDCl 3 ) δ (C), (C), (C), (C), (CH), (CH), (CH), (C), (C), 70.9 (CH 2 ), 59.8 (CH 2 ), 58.5 (CH 3 ), 42.1 (CH), 31.1 (CH 2 ), 29.8 (CH 2 ), 20.7 (CH 2 ), 19.1 (CH 2 ), 14.1 (CH 3 ), 13.7 (CH 3 ). IR (KBr): 2960, 1714, 1635, 1260, 1195, 1150, 1115, 1070, 700 cm 1. MS m/z (%): 344/345/346 (13/3/1) [M + ], 315/316/317 (42/8/2) [M + Et], 301 (100), 77 (3). HRMS Calcd for C 21 H 28 4 : M +, Found: m/z The identity of the regioisomer was confirmed by NE. Ethyl 6-(2-methoxyethyl)-2-methyl-4-phenyl-5-propyl-4H-pyran-3-carboxylate (3ad ). Pr C 2 Et Yield: 37%, colorless oil. TLC: R f 0.50 (hexane/ethyl acetate = 4:1). 1 H NMR (CDCl 3 ) δ (m, 4H; H), 7.16 (m, 1H; H), 4.19 (s, 1H; CH), 4.04 (q, J = 7.0 Hz, 2H; CH 2 ), 3.55 (m, 2H; CH 2 ), 3.36 (s, 3H; CH 3 ), 2.53 (m, 2H; CH 2 ), 2.31 (s, 3H; CH 3 ), 1.91 (m, 1H; CH 2 ), 1.73 (m, 1H; CH 2 ), 1.45 (m, 1H; CH 2 ), 1.23 (m, 1H; CH 2 ), 1.17 (t, J = 7.0 Hz, 3H; CH 3 ), 0.84 (m, 3H; CH 3 ). 13 C NMR (CDCl 3 ) δ (C), (C), (C), (C), (CH), (CH), (CH), (C), (C), 70.1 (CH 2 ), 59.8 (CH 2 ), 58.7 (CH 3 ), 41.4 (CH), 31.2 (CH 2 ), 29.9 (CH 2 ), 21.2 (CH 2 ), 19.2 (CH 3 ), 14.1 (CH 3 ), 14.0 (CH 3 ). IR (KBr): 2960, 1714, 1635, 1140, 1069, 702 cm 1. MS m/z (%): 344/345/346 (20/5/1) [M + ], 315/316/317 (36/7/2) [M + Et], 267 (100), 77 (2). HRMS Calcd for C 21 H 28 4 : M +, Found: m/z The identity of the regioisomer was S5

6 confirmed by NE. Ethyl 5-(methoxymethyl)-2-methyl-4-phenyl-6-propyl-4H-pyran-3-carboxylate (3ae, major). Pr C 2 Et Yield: 53%, orange oil. TLC: R f 0.41 (hexane/ethyl acetate = 4:1). 1 H NMR (CDCl 3 ) δ (m, 4H; H), (m, 1H; H), 4.39 (s, 1H; CH), 4.04 (q, J = 7. 5 Hz, 2H; CH 2 ), 3.86 (d, J = 1 2 Hz, 1H; CH 2 ), 3.63 (d, J = 1 2 Hz, 1H; CH 2 ), 3.26 (s, 3H; CH 3 ), 2.36 (s, 3H; CH 3 ), 2.27 (m, 2H; CH 2 ), 1.60 (m, 2H; CH 2 ), 1.15 (m, 3H; CH 3 ), 0.95 (t, J = 7. 5 Hz, 3H; CH 3 ). 13 C NMR (CDCl 3 ) δ (C), (C), (C), (C), (CH), (CH), (CH), (C), (C), 68.8 (CH 2 ), 59.8 (CH 2 ), 57.5 (CH 3 ), 39.6 (CH), 31.0 (CH 2 ), 20.7 (CH 2 ), 18.9 (CH 3 ), 14.0 (CH 3 ), 13.6 (CH 3 ). IR (KBr): 2960, 1710, 1635, 1447, 1372, 702 cm 1. MS m/z (%): 330/331/332 (8/3/1) [M + ], 285/286/287 (28/5/3) [M + Et], 253 (100), 77 (1). Anal. Calcd for C 20 H 26 4 : C, 72.70; H, 7.93;, Found: C, 72.68; H, 8.08;, The identity of the regioisomer was confirmed by NE. Ethyl 6-(methoxymethyl)-2-methyl-4-phenyl-5-propyl-4H-pyran-3-carboxylate (3ae, minor). Pr C 2 Et Yield: 35%, orange oil. TLC: R f 0.42 (hexane/ethyl acetate = 4:1). 1 H NMR (CDCl 3 ) δ (m, 4H; H), (m, 1H; H), 4.26 (s, 1H; CH), 4.08 (s, 2H; CH 2 ), 4.06 (q, J = 7.0 Hz, 2H; CH 2 ), 3.39 (s, 3H; CH 3 ), 2.37 (s, 3H; CH 3 ), 2.02 (m, 1H; CH 2 ), 1.82 (m, 1H; CH 2 ), 1.50 (m, 1H; CH 2 ), 1.30 (m, 1H; CH 2 ), 1.18 (t, J = 7.0 Hz, 3H; CH 3 ), 0.87 (m, 3H; CH 3 ). 13 C NMR (CDCl 3 ) δ (C), (C), (C), (C), (CH), (CH), (CH), (C), (C), 68.2 (CH 2 ), 60.2 (Ch2), 58.3 (CH 2 ), 41.8 (CH 3 ), 31.2 (CH 2 ), 21.4 (CH 2 ), 19.5 (CH 3 ), 14.4 (CH 3 ), 14.2 (CH 3 ). IR (KBr): 2960, 1733, 1635, 1448, 1371, 1071, 701 cm 1. MS m/z (%): 330/331/332 (14/4/1) [M + ], 301/302/303 (26/5/1) [M + Et], 253 (100), 77 (1). Anal. Calcd for C 20 H 26 4 : C, 72.70; H, 7.93;, Found: C, 72.63; H, 7.96;, The identity of the regioisomer was confirmed by NE. Ethyl 2,5-dimethyl-6-pentyl-4-phenyl-4H-pyran-3-carboxylate and Ethyl 2,6-dimethyl-5- pentyl-4-phenyl-4h-pyran-3-carboxylate (1:1 mixture) (3af). + C 2 Et C 2 Et Yield: 84%, colorless oil. acetate = 4:1). S6 TLC: R f 0.62 (hexane/ethyl 1 H NMR (CDCl 3 ) δ (m, 4H; H), (m, 1H; H), 4.17 (s,0. 5H; CH), 4.06 (s,0. 5H; CH), 4.05 (q, J = 7.0 Hz, 1H; CH 2 ), 4.02 (q, J = 7.0 Hz, 1H; CH 2 ), 2.33 (s,1. 5H; CH 3 ), 2.33 (s,1. 5H; CH 3 ), 2.20 (m, 1H; CH 2 ), 1.90 (m,0. 5H; CH 2 ), 1.89 (s,1. 5H; CH 3 ), 1.72 (m,0. 5H; CH 2 ), 1.53 (m,

7 1H; CH 2 ), 1.49 (s,1. 5H; CH 3 ), (m, 6H; CH 2 CH 2 CH 2 CH 2 ), 1.16 (m, 3H; CH 3 ), 1.16 (m, 3H; CH 3 ), 0.91 (m,1. 5H; CH 3 ), 0.86 (m,1. 5H; CH 3 ). 13 C NMR (CDCl 3 ) δ 167.7/167.6 (C), 159.9/159.7 (C), 146.0/145.6 (C), 144.4/141.3 (C), 128.4/128.3 (CH), 127.9/127.9 (CH), (CH), (C), (C), (C), (C), 59.7/59.7 (CH 2 ), 44.1 (CH), 41.5 (CH), 31.6 (CH 2 ), 31.2 (CH 2 ), 29.3 (CH 2 ), 29.1 (CH 2 ), 27.2 (CH 2 ), 26.9 (CH 2 ), 22.5 (CH 2 ), 22.4 (CH 2 ), 19.2 (CH 3 ), 19.1 (CH 3 ), 15.5 (CH 3 ), 15.2 (CH 3 ), 14.1 (CH 3 ), 14.0 (CH 3 ), 14.0 (CH 3 ). IR (KBr): 2930, 1695, 1575, 1374, 1225, 1063, 699 cm 1. MS m/z (%): 328/329/330 (15/3/1) [M + ], 299/300/301 (20/5/1) [M + Et], 251 (100), 77 (2). HRMS Calcd for C 21 H 28 3 : M +, Found: m/z Ethyl 6-isopropyl-2,5-dimethyl-4-phenyl-4H-pyran-3-carboxylate (3ag). C 2 Et Yield: 55%, colorless oil. TLC: R f 0.61 (hexane/ethyl acetate = 4:1). 1 H NMR (CDCl 3 ) δ (m, 4H; H), (m, 1H; H), 4.04 (q, J = 7.0 Hz, 2H; CH 2 ), 4.03 (s, 1H; CH), 2.79 (qq, J = 6.5, 6.5 Hz, 1H; CH), 2.32 (s, 3H; CH 3 ), 1.49 (s, 3H; CH 3 ), 1.16 (t, J = 7.0 Hz, 3H; CH 3 ), 1.13 (d, J = 6. 5 Hz, 3H; CH 3 ), 1.09 (d, J = 6. 5 Hz, 3H; CH 3 ). 13 C NMR (CDCl 3 ) δ (C), (C), (C), (C), (CH), (CH), (CH), (C), (C), 59.7 (CH 2 ), 44.2 (CH), 27.6 (CH), 19.7 (CH 3 ), 19.7 (CH 3 ), 19.0 (CH 3 ), 15.2 (CH 3 ), 14.1 (CH 3 ). IR (KBr): 2929, 1713, 1635, 1450, 1370, 1256, 1223, 1071, 1022, 699 cm 1. MS m/z (%): 300/301/302 (20/5/1) [M + ], 271/272/273 (17/3/1) [M + Et], 223 (100), 77 (6). Anal. Calcd for C 19 H 24 4 : C, 75.97; H, 8.05;, Found: C, 75.70; H, 8.05;, The identity of the regioisomer was confirmed by NE. Ethyl 2,5-dimethyl-4,6-diphenyl-4H-pyran-3-carboxylate (3ah). C 2 Et Yield: 79%, colorless column. Mp C (ether). TLC: R f 0.40 (hexane/ethyl acetate = 4:1). 1 H NMR (CDCl 3 ) δ (m, 9H; H), (m, 1H; H), 4.22 (s, 1H; CH), 4.07 (q, J = 7.0 Hz, 2H; CH 2 ), 2.40 (s, 3H; CH 3 ), 1.64 (s, 3H; CH 3 ), 1.18 (t, J = 7.0 Hz, 3H; CH 3 ). 13 C NMR (CDCl 3 ) δ (C), (C), (C), (C), (C), (CH), (CH), (CH), (CH), (CH), (CH), (C), (C), 57.9 (CH 2 ), 44.8 (CH), 19.2 (CH 3 ), 17.6 (CH 3 ), 14.1 (CH 3 ). IR (KBr): 2986, 1711, 1634, 1256, 1221, 1072, 694 cm 1. MS m/z (%): 334/335/336 (62/15/2) [M + ], 257/258/259 (100/20/5) [M + Et], 77 (7). HRMS Calcd for C 22 H 20 3 : M +, Found: m/z X-ray single crystal structure analysis (see CIF file). S7

8 Ethyl 5-cyclopropyl-2-methyl-4,6-diphenyl-4H-pyran-3-carboxylate (3ai, major). C 2 Et Yield: 53%, colorless column. Mp C (ether). TLC: R f 0.50 (hexane/ethyl acetate = 4:1). 1 H NMR (CDCl 3 ) δ (m, 2H; H), (m, 5H; H), (m, 2H; H), (m, 1H; H), 4.27 (s, 1H; CH), 4.11 (q, J = 7.0 Hz, 2H; CH 2 ), 2.40 (s, 3H; CH 3 ), 1.39 (m, 1H; CH), 1.22 (t, J = 7.0 Hz, 3H; CH 3 ), 0.60 (m, 1H; CH), 0.48 (m, 1H; CH), 0.27 (m, 1H; CH), 0.22 (m, 1H; CH). 13 C NMR (CDCl 3 ) δ (C), (C), (C), (C), (C), (CH), (CH), (CH), (CH), (CH), (CH), (C), (C), 60.0 (CH 2 ), 41.7 (CH), 19.2 (CH 3 ), 14.2 (CH 3 ), 12.4 (CH), 7.4 (CH 2 ), 7.3 (CH 2 ). IR (KBr): 2926, 1708, 1627, 1445, 1252, 1219, 1205, 1142, 1084, , 710, 694 cm 1. MS m/z (%): 360/361 (14+5) [M + ], 149 (100) [M + Et], 77 (23). HRMS Calcd for C 24 H 24 3 : M +, Found: m/z X-ray single crystal structure analysis (see CIF file). Ethyl 6-cyclopropyl-2-methyl-4,5-diphenyl-4H-pyran-3-carboxylate (3ai, minor). C 2 Et Yield: 15%, colorless oil. TLC: R f 0.50 (hexane/ethyl acetate = 4:1). 1 H NMR (CDCl 3 ) δ (m, 8H; H), (m, 2H; H), 4.44 (s, 1H; CH), 4.05 (q, J = 7.0 Hz, 2H; CH 2 ), 2.32 (s, 3H; CH 3 ), 1.57 (m, 1H; CH), 1.16 (t, J = 7.0 Hz, 3H; CH 3 ), 0.95 (m, 1H; CH), 0.80 (m, 1H; CH), 0.58 (m, 2H; CH,CH). 13 C NMR (CDCl 3 ) δ (C), (C), (C), (C), (C), (CH), (CH), (CH), (CH), (CH), (CH), (C), (C), 60.0 (CH 2 ), 44.3 (CH), 18.9 (CH 3 ), 14.1 (CH 3 ), 10.6 (CH), 5.0 (CH 2 ), 4.7 (CH 2 ). IR (KBr): 2926, 1710, 1635, 1207, 1079, 698 cm 1. MS m/z (%): 360/361/362 (26/7/1) [M + ], 331/332/333 (32/10/1) [M + Et], 283 (100), 77 (8). HRMS Calcd for C 24 H 24 3 : M +, Found: m/z Ethyl 1,3-dimethyl-5,6,7,8-tetrahydro-4aH-isochromene-4-carboxylate (6a). C 2 Et Yield: 92%, colorless oil. TLC: R f 0.85 (hexane/ethyl acetate = 4:1). 1 H NMR (CDCl 3 ) δ 4.17 (q, J = 7.0 Hz, 2H; CH 2 ), 2.99 (m, 1H; CH), 2.38 (m, 1H; CH 2 ), 2.15 (s, 3H; CH 3 ), 1.94 (m, 1H; CH 2 ), (m, 3H; CH 2, CH 2 ), 1.76 (s, 3H; CH 3 ), 1.45 (m, 1H; CH 2 ), 1.30 (m, 1H; CH 2 ), 1.28 (t, J = 7.0 Hz, 3H; CH 3 ), 1.15 (m, 1H; CH 2 ). 13 C NMR (CDCl 3 ) δ (C), (C), (C), (C), (C), 59.6 (CH 2 ), 35.8 (CH), 35.8 (CH 2 ), 29.1 (CH 2 ), 28.2 (CH 2 ), 26.7 (CH 2 ), 19.1 (CH 3 ), 14.6 (CH 3 ), 14.3 (CH 3 ). IR (KBr): 2924, 2853, 2008, 1952, 1708, 1371, 1278, 1184 cm 1. MS m/z (%): 236/237/238 (25/5/1) [M + ], 221/222/223 (100/15/2) [M + Et], 207 (40). HRMS Calcd for C 14 H 20 3 : M +, Found: m/z S8

9 Ethyl 3-methyl-1-phenyl-5,6,7,8-tetrahydro-4aH-isochromene-4-carboxylate (6b). C 2 Et Yield: 99%, pale yellow oil. TLC: R f 0.45 (hexane/ethyl acetate = 9:1). 1 H NMR (CDCl 3 ) δ (m, 5H; H), 4.22 (q, J = 7.0 Hz, 2H; CH 2 ), 3.21 (m, 1H; CH), 2.53 (m, 1H; CH 2 ), 2.22 (s, 3H; CH 3 ), 2.06 (m, 1H; CH 2 ), (m, 3H; CH 2, CH 2 ), 1.55 (m, 1H; CH 2 ), (m, 2H; CH 2 ), 1.31 (t, J = 7.0 Hz, 3H; CH 3 ). 13 C NMR (CDCl 3 ) δ (C), (C), (C), (C), (CH), (CH), (CH), (C), (C), 59.8 (CH 2 ), 36.6 (CH), 36.1 (CH 2 ), 29.4 (CH 2 ), 28.6 (CH 2 ), 26.6 (CH 2 ), 19.2 (CH 3 ), 14.3 (CH 3 ). IR (KBr): 2927, 2854, 1714, 1634, 1245, 1075, 699 cm 1. MS m/z (%): 298/299/300 (80/15/2) [M + ], 269/270/271 (100/17/2) [M + Et], 77 (18). HRMS Calcd for C 19 H 22 3 : M +, Found: m/z xa-nickelacycle (4a). Experimental procedure. A solution of TMEDA (75µL, 0.50 mmol) in toluene (5 ml) was added dropwise to a solution of Ni(cod) 2 (13.8 mg, 0.05 mmol) in toluene (5mL). The resulting yellow solution was stirred at room temperature for 5 min. To this solution was added dropwise a solution of 1a (109 mg, 0.05 mmol) in 5mL toluene, and the resulting red solution was stirred at room temperature for 2 h. Toluene was evaporated. The precipitate was further crystallized in toluene at 30 C. The red crystalline solid was washed with hexane and dried in vacuo to yield 2 (215 mg, 98%). This complex crystallized with 0.5 equiv of toluene/molecule of 4a in the lattice. In the crystallographic analysis, the lattice contained a disordered and ill-defined solvent region that could not be reasonably assigned in the crystallographic model. 1 H NMR (toluene-d 8 ) δ (m, 5H; H), 4.05 (m, 2H; CH 2 ), 2.85 (s, 1H; CH), 2.51 (s, 3H; CH 3 ), (m, 12H; CH 3, CH 3, CH 3, CH 3 ), 1.75 (br, 4H; CH 2, CH 2 ), 1.05 (m, 3H; CH 3 ). 13 C NMR (toluene-d 8 ) δ (C), (C), (C), (C), (CH), (CH), (CH), 61.6 (CH 2 ), 57.3 (CH), 55.3 (CH 2 ), 50.1 (CH 2 ), 48.4 (CH 3 ), 45.3 (CH 3 ), 45.1 (CH 3 ), 33.9 (CH 3 ), 22.5 (CH 3 ), 15.0 (CH 3 ). X-ray single crystal structure analysis (see CIF file). S9

10 RTEP drawing: 3ah Empirical formula C22 H22 3 Formula weight Temperature Wavelength Crystal system Space group 273(2) K Å Monoclinic P2(1)/c Unit cell dimensions a = (5) Å α= 90. b = 9.537(4) Å β= (6). c = (5) Å γ = 90. Volume (11) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 712 Crystal size 1.00 x 0.50 x 0.20 mm 3 Theta range for data collection 1.57 to Index ranges -18<=h<=18, -5<=k<=12, -16<=l<=18 Reflections collected Independent reflections 3999 [R(int) = ] Completeness to theta = % Absorption correction None Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3999 / 0 / 229 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S10

11 RTEP drawing: 3ai, major Empirical formula C24 H24 3 Formula weight Temperature Wavelength Crystal system Space group 299(2) K Å Monoclinic P2(1)/c Unit cell dimensions a = (8) Å α= 90. b = 9.394(5) Å β= (8). c = (8) Å γ = 90. Volume (17) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 768 Crystal size 0.20 x 0.15 x 0.10 mm 3 Theta range for data collection 2.61 to Index ranges -13<=h<=18, -12<=k<=11, -19<=l<=12 Reflections collected Independent reflections 4195 [R(int) = ] Completeness to theta = % Absorption correction None Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4195 / 0 / 246 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S11

12 RTEP drawing: 4a Empirical Formula C H 30 N 2 3 Ni Formula Weight Crystal Color, Habit Crystal Dimensions Crystal System Lattice Type Detector Position Pixel Size Lattice Parameters orange, plate 0.15 X 0.15 X 0.10 mm triclinic Primitive mm mm a = (18) Å b = (17) Å c = (15) Å α = (8) o β = (8) o γ = (9) o V = (3) Å 3 Space Group P-1 (#2) Z value 2 Dcalc g/cm 3 F µ(mokα) cm -1 Detector Rigaku Saturn Goniometer Rigaku AFC10 Radiation MoKα (λ = Å) graphite monochromated Detector Aperture Data Images ω oscillation Range (χ=45.0, φ=0.0) Exposure Rate 70 mm x 70 mm 720 exposures o 40.0 sec./ o S12

13 Detector Swing Angle ω oscillation Range (χ=45.0, φ=90.0) Exposure Rate Detector Swing Angle Detector Position o o 40.0 sec./ o o mm Pixel Size mm 2θmax 55.0 o No. of Reflections asured Total: 8219 Unique: 4785 (Rint = 0.021) Corrections Lorentz-polarization Absorption (trans. factors: ) Structure Solution Direct thods (SAPI91) Refinement Full-matrix least-squares on F 2 Function Minimized Σ w (Fo 2 - Fc 2 ) 2 Least Squares Weights 1/[0.0020Fo σ(Fo 2 )]/(4Fo 2 ) 2θmax cutoff 55.0 o Anomalous Dispersion All non-hydrogen atoms No. bservations (All reflections) 4785 No. Variables 280 Reflection/Parameter Ratio Residuals: R1 (I>2.00σ(I)) Residuals: R (All reflections) Residuals: wr2 (All reflections) Goodness of Fit Indicator Max Shift/Error in Final Cycle Maximum peak in Final Diff. Map 1.04 e - /Å 3 Minimum peak in Final Diff. Map e - /Å 3 S13

14 3aa S14

15 3ea S15

16 3fa S16

17 3ga S17

18 3ab S18

19 3ac S19

20 3ad S20

21 Pr Et H H NE 2.3% S21

22 3ad S22

23 Et H H NE 4.9% S23

24 3ae, major S24

25 Pr Et H H NE 2.3% S25

26 3ae, minor S26

27 Et H H NE 1.0% S27

28 3af S28

29 3ag S29

30 i Pr Et H H NE 9.3% S30

31 3ah S31

32 Et H H NE 5.6% S32

33 3ai, major S33

34 3ai, minor S34

35 6a S35

36 6b S36

37 4a S37