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1 Supporting Information Regioselective Reversal in the Cyclization of 2-Diazo-3,5-dioxo-6-ynoates (ynones, ynamide): Construction of -Pyrones and 3(2H)-Furanones Starting from Identical Materials Feng Wang, Shengle Lu, Bo Chen, Yali Zhou, Ying Yang, and Guisheng Deng* Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), Hunan Normal University, Changsha , China; Key Laboratory of the Assembly and Application of rganic Functional Molecules, Hunan Normal University, Changsha , China. * Additional Supporting Information files

2 Table of Contents 1. Materials and methods General methods General procedure for the preparation of substrate Typical procedure for preparation of compound 10 and general experimental information Typical procedure for oxidation of compound 10 for synthesis of compound 1 and general experimental information General procedure for regioselective synthesis of -pyrones 2 (Method A) and 3(2H)-furanones 3 (Method B) Typical procedure for the Rh 2 (Ac) 4 -catalyzed reaction of 2b Single crystal data about 2n Single crystal data about 3e References H-NMR and 13 C-NMR spectrum for all new products...54

3 1. Materials and methods 1.1 General methods All reactions were carried out in a round flask with magnetic stirring. All alkynals were prepared according to the method in literature. 1 Unless otherwise noted, all experiments were performed under air atmosphere. Unless otherwise noted, all reagents and solvents were purchased from Aladdin, Energy Chemical for direct use. Dry DCM and dry THF were obtained by treatment with CaH 2 and sodium, respectively, and distilled prior to use. Purifications of reaction products were carried out by flash chromatography using Qingdao Haiyang Chemical Co. Ltd silica gel ( mesh). Infrared spectra (IR) were recorded on a Nicolet Nexus TT-IR spectrophotometer and are reported as wavelength numbers (cm -1 ). Infrared spectra were recorded by preparing a KBr pellet containing the title compound. 1 H NMR and 13 C NMR spectra were recorded on a Bruker Avance-500 Spectrometer in CDCl 3 solution using tetramethylsilane as an internal standard. MS (FAB) and HRMS spectra were recorded on Waters ZQ2000 and Bruker APEX IV, respectively. For thin layer chromatography (TLC) analysis throughout this work, Merck 25 TLC aluminium sheets (silica gel 60 GF254, 0.25 mm) were used. Chemical shifts are reported in parts per million (ppm) and coupling constants are reported as Hertz (Hz). Splitting patterns are designated as singlet (s), broad singlet (bs), doublet (d), triplet (t). Splitting patterns that could not be interpreted or easily visualized are designated as multiple (m). MS (FAB) and HRMS spectra were recorded on Waters ZQ2000 and Bruker APEX IV, respectively. X-ray data were taken on a Rigaku Supernova diffractometer equipped with an ES S2 CCD detector. 1.2 General procedure for the preparation of substrate 1 R 1 N R 2 2 CH 9 8a: R 1 = Et 8b: R 1 = Ph 1) TiCl 4, Et 3 N H 10 R 1 [] 2) R 2 R 2 1 R 1

4 1.2.1 Typical procedure for preparation of compound 10 and general experimental information TiCl 4 (209 mg, 1.1 mmol) and Et 3 N (111 mg, 1.1 mmol) were syringed dropwise into a vigorous stirring solution of 8a (156 mg, 1 mmol) in anhydrous CH 2 Cl 2 (10 ml) at 78 o C under nitrogen atmosphere. The dark-red mixture was stirred at 78 o C for 1 h. 2 9a (R 1 = Ph, 131 mg, 1 mmol) in anhydrous CH 2 Cl 2 (2 ml) were added to this mixture by syringe. The reaction mixture was stirred for another 8 h and then quenched with saturated aqueous NH 4 Cl (5 ml). The organic layer was separated, washed with saturated aqueous NaHC 3 (10 ml), dried over anhydrous Na 2 S 4 and then concentrated in vacuum. The product was purified by flash chromatography to yield 10a (R 1 = Et, R 2 = Ph) as an oil (246 mg) in 86% yield. The results are summarized in Table S-1. Table S-1. entry substrate 9 8 t (h) product 10 yield a (%) 1 CH 9a Et 8a H 6 Et Ph 10a 86 2 CH9b Et 8a H 6 Et p-mec 6 H 4 10b 90 3 n-pr CH 9c Et 8a H 6 Et p-n-prc 6 H 4 10c 91 H Bu t CH 4 Bu t 9d Et 8a 5.5 Bu t Bu t Et 10d 80 CH CH 5 3 9e Et 8a H 6 Et p-mec 6 H 4 10e 80 Cl CH 6 9f Et 8a H 6 Et p-clc 6 H 4 10f 76

5 7 F CH 9g Et 8a H 6 Et p-fc 6 H 4 10g 75 8 CH 9a Ph 8b H 6 Ph Ph 10h 88 9 CH 9b Ph 8b H 6 Ph p-mec 6 H 4 10i n-pr CH 9c Ph 8b H 6 Ph p-n-prc 6 H 4 10j 90 CH 11 CH 3 9e Ph 8b H 6 Ph p-mec 6 H 4 10k 80 Cl CH 12 9f Ph 8b H 6 Ph p-clc 6 H 4 10l 73 F CH 13 9g 14 CH 9b Ph N Bn 8b 8c H 6 Ph p-fc 6 H 4 10m H 72 6 N 59 p-mec 6 H 4 Bn 10n 15 Ph CH 9h Et 8a 6 Ph H Et 10o CH 3 (CH 2 ) 6 9i CH Et 8a 6 CH 3 (CH 2 ) 6 H Et 10p CH 9j Et 8a 6 H Et 10q CH S 9k Et 8a 6 H Et S 10r CH Et 9l 8a H 6 Et 10s n-bu CH 9m Et 8a H 6 Et n-bu 10t 85

6 21 n-bu CH 9m Ph 22 Me 3 Si CH 9n Et 8b 8a H 6 Ph n-bu H 6 Et Me 3 Si 10u 10v H Ph Et Ethyl 2-diazo-5-hydroxy-3-oxo-7-phenylhept-6-ynoate (10a). 3 Yellow liquid (246 mg, 86%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ (m, 2H), (m, 3H), (m, 1H), 4.31 (q, J = 7.0 Hz, 2H), 3.51 (dd, J = 17.5, 8.0 Hz, 1H), 3.34 (d, J = 6.0 Hz, 1H), 3.29 (dd, J = 17.5, 3.5 Hz 1H), 1.33 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 190.8, 160.9, 131.6, 128.3, 128.1, 122.3, 88.4, 84.7, 61.6, 58.96, 47.0, 30.8, H Et p-mec 6 H 4 Ethyl 2-diazo-5-hydroxy-3-oxo-7-p-tolylhept-6-ynoate (10b). 3 Yellow liquid (270 mg, 90%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.31 (d, J = 8.0 Hz, 2H), 7.09 (d, J = 8.0 Hz, 2H), 5.08 (dd, J = 8.5, 3.5 Hz, 1H), 4.31 (q, J = 7.0 Hz, 2H), 3.50 (dd, J = 17.5, 8.5 Hz, 1H), 3.28 (dd, J = 17.5, 3.5 Hz, 1H), 2.33 (s, 1H), 1.33 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 191.0, 161.1, 138.6, 131.7, 129.0, 119.4, 87.7, 85.1, 76.8, 61.73, 59.3, 47.2, 21.4, H Et p-n-prc 6 H 4 Ethyl 2-diazo-5-hydroxy-3-oxo-7-(4-propylphenyl)hept-6-ynoate (10c). 3 Yellow liquid (311 mg, 91%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.33 (d, J = 8.0 Hz, 2H), 7.09 (d, J = 8.0 Hz, 2H), (m, 1H), 4.30 (q, J = 7.0 Hz, 2H), 3.50 (dd, J = 17.5, 8.5 Hz, 1H), 3.35 (d, J = 6.0 Hz, 1H), 3.27 (dd, J = 17.5, 3.5 Hz, 1H), 2.55 (t, J = 7.5 Hz, 2H), (m, 2H), 1.32 (t, J = 7.0 Hz, 3H), 0.91 (t, J = 7.5 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 190.9, 161.0, 143.3, 131.6, 128.3, 119.5, 87.7,

7 85.1, 76.7, 61.7, 59.2, 47.1, 37.8, 24.2, 14.2, H Bu t Et Bu t Ethyl 7-(3,5-di-tert-butylphenyl)-2-diazo-5-hydroxy-3-oxohept-6-ynoate (10d). 3 Yellow liquid (263 mg, 80%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.36 (d, J = 1.5 Hz, 1H), 7.28 (d, J = 1.5 Hz, 2H), 5.12 (dd, J = 8.5, 3.5 Hz, 1H), 4.30 (q, J = 7.0 Hz, 2H), 3.53 (dd, J = 17.5, 8.5 Hz, 1H), 3.31 (dd, J = 17.5, 3.5 Hz, 1H), 1.31 (t, J = 7.0 Hz, 3H), 1.29 (s, 18H). 13 C-NMR (125.8 MHz, CDCl 3, ppm ) δ 190.9, 161.0, 150.6, 125.9, 122.7, 121.3, 87.1, 85.9, 61.6, 59.1, 47.1, 34.6, 31.2, H Et p-mec 6 H 4 Ethyl 2-diazo-5-hydroxy-7-(4-methoxyphenyl)-3-oxohept-6-ynoate (10e). 3 Yellow liquid (263 mg, 80%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.35 (d, J = 9.0 Hz, 2H), 6.81 (d, J = 9.0 Hz, 2H), (m, 1H), 4.30 (q, J = 7.0 Hz, 2H), 3.79 (s, 1H), 1.49 (dd, J = 17.5, 8.5 Hz, 1H), 3.27 (dd, J = 17.5, 3.5 Hz, 1H), 3.27 (d, J = 6.0 Hz, 1H), 1.33 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 191.0, 161.0, 159.7, 133.2, 114.5, 113.8, 87.0, 84.9, 76.8, 61.7, 59.2, 55.2, 47.2, H Et p-clc 6 H 4 Ethyl 7-(4-chlorophenyl)-2-diazo-5-hydroxy-3-oxohept-6-ynoate (10f). 3 Yellow liquid (243 mg, 76%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.35 (d, J = 8.5 Hz, 2H), 7.27 (d, J = 8.5 Hz, 2H), (m, 1H), 4.31 (q, J = 7.0 Hz, 2H), 3.50 (dd, J = 17.5, 8.0 Hz, 1H), 3.48 (d, J = 6.0 Hz, 1H), 3.29 (dd, J = 17.5, 3.5 Hz, 1H), 1.34 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 190.9, 161.0, 134.4, 132.9, 128.5, 120.8, 59.3, 83.7, 76.7, 61.7, 59.0, 46.9, H Et p-fc 6 H 4 Ethyl 2-diazo-7-(4-fluorophenyl)-5-hydroxy-3-oxohept-6-ynoate (10g). 3 Yellow

8 liquid (228 mg, 75%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.37 (dd, J = 9.0, 5.5 Hz, 2H), 6.95 (dd, J = 9.0, 8.5 Hz, 2H), (m, 1H), 4.27 (q, J = 7.0 Hz, 2H), 3.51 (d, J = 5.5 Hz, 1H), 3.47 (dd, J = 17.5, 8.5 Hz, 1H), 3.26 (dd, J = 17.5, 3.5 Hz, 1H), 1.29 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 190.8, 163.4, (d, J = 60.5 Hz), (d, J = 8.25 Hz), (d, J = 3.5 Hz), (d, J = 22.0 Hz), 88.1, 83.7, 77.20, 61.6, 58.9, 46.9, Ph H Ph 2-Diazo-5-hydroxy-1,7-diphenylhept-6-yne-1,3-dione (10h). 3 Yellow liquid (280 mg, 88%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ (m, 2H), (m, 1H), 7.47 (t, J = 7.5 Hz, 2H), (m, 2H), (m, 3H), 5.15 (dd, J = 8.0, 4.0 Hz, 1H), 3.61 (dd, J = 17.5, 8.0 Hz, 1H), 3.60 (s, 1H), 3.39 (dd, J = 17.5, 4.0 Hz, 1H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 191.4, 184.8, 136.9, 132.8, 131.7, 128.9, 128.4, 128.1, 127.3, 122.3, 88.5, 84.9, 83.9, 59.2, H Ph p-mec 6 H 4 2-Diazo-5-hydroxy-1-phenyl-7-p-tolylhept-6-yne-1,3-dione (10i). 3 Yellow liquid (295 mg, 89%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.62 (d, J = 7.5 Hz, 2H), 7.56 (t, J = 7.5 Hz, 1H), 7.46 (t, J = 7.5 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 7.07 (d, J = 8.0 Hz, 2H), 5.14 (dd, J = 8.0, 4.0 Hz, 1H), 3.60 (s, 1H), 3.59 (dd, J = 17.0, 8.0 Hz, 1H), 3.38 (dd, J = 17.0, 4.0 Hz, 1H), 2.31 (s, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 191.4, 184.8, 138.4, 136.8, 132.8, 131.5, 128.8, 128.8, 127.3, 119.1, 87.8, 85.0, 83.7, 59.2, 48.1, H p-n-prc 6 H 4 Ph 2-Diazo-5-hydroxy-1-phenyl-7-(4-propylphenyl)hept-6-yne-1,3-dione (10j). 3 Yellow liquid (324 mg, 90%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.63 (d, J = 7.5 Hz, 2H), 7.56 (t, J = 7.5 Hz, 1H), 7.46 (t, J = 7.5 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 7.08 (d, J = 8.0 Hz, 2H), 5.15 (dd, J = 8.0, 4.0 Hz, 1H), 3.61 (dd, J = 17.0, 8.0 Hz, 1H),

9 3.39 (dd, J = 17.0, 4.0 Hz, 1H), 2.54 (t, J = 7.5 Hz, 2H), (m, 2H), 0.90 (t, J = 7.5 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 191.4, 184.8, 143.2, 136.8, 132.8, 131.5, 128.8, 128.3, 127.3, 119.4, 87.7, 85.1, 84.0, 59.2, 48.1, 37.8, 24.1, H Ph p-mec 6 H 4 2-Diazo-5-hydroxy-7-(4-methoxyphenyl)-1-phenylhept-6-yne-1,3-dione (10k). 3 Yellow liquid (278 mg, 80%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ (m, 2H), (m, 1H), 7.46 (t, J = 7.5 Hz, 2H), (m, 2H), (m, 2H), 5.12 (dd, J = 8.0, 3.5 Hz, 1H), 3.76 (s, 3H), 3.58 (dd, J = 17.5, 8.0 Hz, 1H), 3.55 (s, 1H), 3.37 (dd, J = 17.5, 3.5 Hz, 1H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 191.4, 184.8, 159.6, 136.8, 133.1, 132.8, 128.8, 127.3, 114.3, 113.7, 87.1, 84.8, 83.9, 59.2, 55.1, H Ph p-clc 6 H 4 7-(4-Chlorophenyl)-2-diazo-5-hydroxy-1-phenylhept-6-yne-1,3-dione (10l). 3 Yellow liquid (184 mg, 73%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.64 (d, J = 7.5 Hz, 2H), 7.60 (t, J = 7.5 Hz, 1H), 7.50 (t, J = 7.5 Hz, 2H), 7.36 (d, J = 7.5 Hz, 2H), 7.27 (d, J = 7.5 Hz, 2H), 5.13 (t, J = 3.5 Hz, 1H), 3.60 (dd, J = 17.5, 8.0 Hz, 1H), 3.43 (d, J = 3.5 Hz, 1H), 3.41 (dd, J = 17.5, 4.0 Hz, 1H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 191.6, 184.9, 136.9, 134.5, 133.0, 129.0, 128.6, 127.6, 127.4, 120.8, 89.4, 83.9, 76.9, 59.3, H Ph p-fc 6 H 4 2-Diazo-7-(4-fluorophenyl)-5-hydroxy-1-phenylhept-6-yne-1,3-dione (10m). 3 Yellow liquid (242 mg, 72%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.60 (d, J = 7.5 Hz, 2H), 7.52 (t, J = 7.5 Hz, 1H), 7.42 (t, J = 7.5 Hz, 2H), 7.35 (dd, J = 8.5, 5.5 Hz, 2H), 6.92 (t, J = 8.5 Hz, 2H), 5.13 (dd, J = 8.5, 3.5 Hz, 1H), 3.57 (dd, J = 17.5, 8.5 Hz, 1H), 3.38 (dd, J = 17.5, 3.5 Hz, 1H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 191.1, 184.7,

10 163.3, 161.3, 136.7, (d, J = 8.25 Hz), 132.7, 128.8, 127.2, (d, J = 3.5 Hz), (d, J = 22.13), 88.3, 83.8 (d, J = 17.5 Hz), 58.0, H p-mec 6 H 4 Bn N 1-(5-benzyl-2-oxooxazolidin-3-yl)-2-diazo-5-hydroxy-7-p-tolylhept-6-yne-1,3-dion e (10n). Yellow liquid (254 mg, 59%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ (m, 5H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 3.55 (dd, J = 17.0, 8.5 Hz, 1H), 3.40 (dd, J = 17.0, 8.5 Hz, 1H), 3.28 (dd, J = 13.5, 3.5 Hz, 1H), 3.21 (dd, J = 17.0, 3.5 Hz, 1H), 2.90 (dd, J = 13.5, 9.0 Hz, 1H), (m, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 190.3, 159.5, 159.4, 152.6, 138.5, 134.4, 131.5, 129.1, 128.9, 127.5, 119.2, 87.7, 85.0, 80.0, 67.1, 59.3, 55.4, 47.7, 37.4, IR (KBr): 3497, 3025, 2921, 2855, 2228, 2137, 1772, 1669, 1507, 1328, 1216, 1104, 809, 743, 697 cm -1. HRMS calcd for [M] + C 24 H 21 N 3 5 : , found: H Ph Et (E)-Ethyl 2-diazo-5-hydroxy-3-oxo-9-phenylnon-8-en-6-ynoate (10o). Yellow liquid (187 mg, 60%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ (m, 5H), 6.95 (d, J = 15.0 Hz, 1H), 6.16 (d, J = 15.0 Hz, 1H), 5.04 (s, 1H), 4.30 (q, J = 7.0 Hz, 2H), 3.47 (dd, J = 17.5, 8.0 Hz, 1H), 3.26 (dd, J = 17.5, 3.5 Hz, 1H), 1.31 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm ) δ 190.7, 160.9, 141.8, 135.9, 128.6, 126.9, 126.2, 107.3, 90.6, 84.0, 61.6, 59.1, 47.0, IR(KBr): 3417, 2193, 2138, 1716, 1636, 1617, 1457, 1385, 1191, 472 cm -1. MS (EI) m/z: 284 (M + - ), 256, 235, 209, 196, 165, 140, 128, 115, 91, 69, 58, 43. HRMS calcd for [M] + C 17 H 16 4 : , found: H Et CH 3 (CH 2 ) 6 (E)-Ethyl 2-diazo-5-hydroxy-3-oxohexadec-8-en-6-ynoate (10p). Yellow liquid (224 mg, 67%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ (m, 1H), 5.44 (d, J =

11 15.0 Hz, 1H), 4.93 (s, 1H), 4.29 (q, J = 7.0 Hz, 2H), 3.39 (dd, J = 17.5, 8.0 Hz, 1H), 3.18 (dd, J = 17.5, 3.5 Hz, 1H), 2.07 (m, 2H), (m, 13H), 0.85 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 191.0, 161.0, 145.8, 108.6, 86.7, 83.8, 76.8, 61.6, 59.1, 47.1, 33.0, 31.7, 29.0, 29.0, 28.6, 22.6, 14.2, IR (KBr): 3750, 3446, 2926, 2855, 2137, 1717, 1652, 1457, 1384, 1305, 1215, 1193, 1133, 1050, 563 cm -1. MS (EI) m/z: 306 (M + - ), 277, 207, 179, 161, 134, 105, 91, 81, 55, 43. HRMS calcd for [M] + C 18 H 26 4 : , found: H Et Ethyl 2-diazo-5-hydroxy-9-methyl-3-oxodec-8-en-6-ynoate (10q). Yellow liquid (145 mg, 55%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ 5.23 (s, 1H), 4.97 (s, 1H), 4.30 (q, J = 7.0 Hz, 2H), 3.43 (dd, J = 17.5, 8.0 Hz, 1H), 3.19 (dd, J = 17.5, 3.5 Hz, 1H), 1.85 (s, 3H), 1.77 (s, 3H) 1.32 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm ) δ 191.0, 161.0, 149.4, 104.4, 90.3, 83.0, 61.6, 59.3, 47.2, 24.7, 20.9, IR (KBr): 3412, 2975, 2188, 2133, 1717, 1637, 1457, 1385, 1088, 1048, 880, 617 cm -1. MS (EI) m/z: 236 (M + - ), 193, 175, 149, 109, 91, 83, 65, 55, 43. HRMS calcd for [M] + C 13 H 16 4 : , found: H Et S Ethyl 2-diazo-5-hydroxy-3-oxo-7-(thiophen-3-yl)hept-6-ynoate (10r). 3 Yellow liquid (219 mg, 75%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.34 (d, J = 3.0 Hz, 1H), 7.15 (dd, J = 5.0, 3.0 Hz, 1H), 6.99 (d, J = 5.0 Hz, 1H), 5.01 (dd, J = 8.0, 4.0 Hz, 1H), 4.19 (q, J = 7.0 Hz, 2H), 3.41 (dd, J = 17.0, 8.0 Hz, 1H), 3.19 (dd, J = 17.0, 4.0 Hz, 1H), 1.21 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm ) δ 190.5, 161.0, 129.8, 129.1, 125.3, , 88.5, 79.9, 77.6, 61.7, 58.9, 47.2, H Et Ethyl 7-cyclopropyl-2-diazo-5-hydroxy-3-oxohept-6-ynoate (10s). 3 Yellow liquid

12 (200 mg, 80%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ 4.79 (d, J = 6.5 Hz, 1H), 4.30 (q, J = 7.0 Hz, 2H), 3.33 (dd, J = 17.5, 8.5 Hz, 1H), 3.14 (dd, J = 17.5, 3.5 Hz, 1H), 3.08 (s, 1H), 1.32 (t, J = 7.0 Hz, 3H), (m, 1H), (m, 2H), (m, 2H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 191.1, 161.1, 88.8, 74.7, 66.9, 61.7, 58.9, 47.4, 14.3, 8.2, n-bu H Et Ethyl 2-diazo-5-hydroxy-3-oxoundec-6-ynoate (10t). 3 Yellow liquid (226 mg, 85%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ (m, 1H), 4.30 (q, J = 7.0 Hz, 2H), 3.36 (dd, J = 17.5, 8.5 Hz, 1H), 3.16 (dd, J = 17.5, 3.5 Hz, 1H), 3.07 (d, J = 6.0 Hz, 1H), (m, 2H), (m, 2H), (m, 2H), 1.33 (t, J = 7.0 Hz, 3H), 0.90 (t, J = 7.0 HZ, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 191.0, 161.0, 87.0, 79.5, 76.7, 61.6, 58.7, 47.4, 30.5, 21.8, 18.2, 14.2, n-bu H Ph 2-Diazo-5-hydroxy-1-phenylundec-6-yne-1,3-dione (10u). 3 Yellow liquid (263 mg, 88%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ (m, 2H), (m, 1H), 7.47 (t, J = 7.5 Hz, 2H), 4.87 (s, 1H), 3.43 (dd, J = 17.5, 8.0 Hz, 1H), 3.26 (d, J = 4.0 Hz, 1H), 3.25 (dd, J = 17.5, 3.5 Hz, 1H), 2.17 (td, J = 7.0, 2.0 Hz, 2H), (m, 2H), (m, 2H), 0.87 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 191.8, 184.8, 136.9, 132.9, 128.9, 127.3, 85.9, 79.4, 76.8, 59.0, 48.4, 30.5, 21.8, 18.3, H Me 3 Si Et Ethyl 2-diazo-5-hydroxy-3-oxo-7-(trimethylsilyl)hept-6-ynoate (10v). Yellow liquid (124 mg, 44%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ 4.83 (t, J = 4.5 Hz, 1H), 4.28 (q, J = 7.0 Hz, 2H), 3.37 (dd, J = 17.5, 8.5 Hz, 1H), 3.21 (d, J = 4.5 Hz, 1H), 3.14 (dd, J = 17.5, 3.5 Hz, 1H), 1.31 (t, J = 7.0 Hz, 3H), 0.12 (s, 9H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 190.8, 161.0, 104.7, 89.6, 76.9,61.6, , 14.2, IR (KBr): 3514, 2966, 2893, 2236, 2128, 1711, 1654, 1641, 1373, 1303, 1070

13 cm -1. MS (EI) 282(M + ), 253, 239, 210, 195, 167, 151, 137, 125, 111, 99, 84, 75(100), 59, 45. HRMS calcd for [M] + C 12 H 18 4 Si: , found: Typical procedure for oxidation of compound 10 for synthesis of compound 1 and general experimental information DMP (4 mmol, g) was added to a solution of 10a (2 mmol, g) in anhydrous CH 2 Cl 2 (20 ml). The mixture was stirred at room temperature for 48 h. The reaction mixture was separated by suction filtration. The filtrate was concentrated in vacuum, and the residue was purified by flash chromatography to yield 1a (R 1 = Et, R 2 = Ph) as a faint yellow solid (156 mg) in 55% yield. The results are summarized in Table S-2. Table S-2. xidation of compound 10 into compound 1 entry substrance 10 t (h) product 1 H 1 Et Ph 10a 2 Et p-mec 6 H 4 H 3 Et p-n-prc 6 H 4 4 H 48 Et Ph H H H Et Bu t 10b 10c 1a 48 Et p-mec 6 H 4 H 48 Et p-n-prc 6 H 4 48 Bu t H Et 1b 1c yield a (%) Bu t 10d Bu t 1d H 5 Et p-mec 6 H 4 10e H 6 Et p-clc 6 H 4 10f H 48 Et p-mec 6 H 4 H 48 Et p-clc 6 H 4 1e 1f 55 54

14 H 7 Et p-fc 6 H 4 10g H 8 Ph Ph 10h H 48 Et p-fc 6 H 4 H 48 Ph Ph 1h 1g H 9 Ph p-mec 6 H 4 10i H 10 Ph p-n-prc 6 H 4 H 11 Ph p-mec 6 H 4 H 12 Ph 10j 10k p-clc 6 H 4 10l H 13 Ph p-fc 6 H 4 10m H 48 Ph p-mec 6 H 4 H 48 Ph p-n-prc 6 H 4 H 48 Ph p-mec 6 H 4 H 48 Ph p-clc 6 H 4 H 48 Ph p-fc 6 H 4 14 N 48 N 29 p-mec 6 H 4 p-mec 6 H 4 10n 1n Ph CH 3 (CH 2 ) 6 H H H H Bn H Et 10o Et 10p Et 10q Et S 10r H 19 Et Ph CH 3 (CH 2 ) 6 S H H H 1p Bn H H H Et Et Et 10s 48 Et 1i 1j 1k 1l 1m 1o Et 1q 1r 1s

15 H 20 Et n-bu 10t H 4.5 Et n-bu 1t 59 b H 21 Ph n-bu 10u H 48 Ph n-bu 1u 40 H 22 Et Me 3 Si 10v H 48 Et Me 3 Si 1v 49 a Isolated yield. b The compound was oxidized by Jones Reagent. H Ph Et (Z)-Ethyl 2-diazo-3-hydroxy-5-oxo-7-phenylhept-3-en-6-ynoate (1a). 3 Yellow solid (156 mg, 55%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), (m, 2H), (m, 3H), 6.86 (s, 1H), 4.31(q, J = 7.0 Hz, 2H), 1.32 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.8, 160.6, 158.6, 133.2, 132.4, 130.1, 128.5, 120.5, 94.5, 84.2, 74.4, 61.6, H Et p-mec 6 H 4 (Z)-Ethyl 2-diazo-3-hydroxy-5-oxo-7-p-tolylhept-3-en-6-ynoate (1b). 3 Yellow solid (170 mg, 57%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 7.43 (d, J = 8.0 Hz, 2H), 7.16 (d, J = 8.0 Hz, 2H), 6.84 (s, 1H), 4.31 (q, J = 7.0 Hz, 2H), 1.33 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 180.6, 160.7, 158.9, 140.7, 132.3, 129.3, 117.4, 102.5, 95.6, 83.8, 74.3, 61.6, 21.6, H Et p-n-prc 6 H 4 (Z)-Ethyl 2-diazo-3-hydroxy-5-oxo-7-(4-propylphenyl)hept-3-en-6-ynoate (1c). 3 Yellow solid (187 mg, 55%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 14.61

16 (s, 1H), 7.46 (d, J = 8.0 Hz, 2H), 7.80 (d, J = 8.0 Hz, 2H), 6.85 (s, 1H), 4.32 (q, J = 7.0 Hz, 2H) 2.60 (t, J = 7.5 Hz, 2H), (m, 2H), 1.35 (t, J = 7.0 Hz, 3H), 0.94 (t, J = 7.5 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.6, 160.8, 159.1, 145.5, 132.5, 128.7, 117.8, 102.6, 95.3, 84.0, 74.4, 61.8, 56.0, 38.1, 24.2, 14.3, H Bu t Et Bu t (Z)-Ethyl 7-(3,5-di-tert-butylphenyl)-2-diazo-3-hydroxy-5-oxohept-3-en-6-ynoate (1d). 3 Yellow solid (141 mg, 50%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 7.49 (s, 1H), 7.42 (s, 2H), 6.89 (s, 1H), 4.34 (q, J = 7.0 Hz, 2H), 1.34 (t, J = 7.0 Hz, 3H), 1.32 (s, 18). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.7, 160.8, 159.2, 151.2, 126.9, 124.8, 119.6, 102.6, 96.4, 83.4, 61.7, 34.9, 31.3, H Et p-mec 6 H 4 (Z)-Ethyl 2-diazo-3-hydroxy-7-(4-methoxyphenyl)-5-oxohept-3-en-6-ynoate (1e). 3 Yellow solid (173 mg, 55%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 7.48 (d, J = 8.0 Hz, 2H), 6.87 (d, J = 8.0 Hz, 2H), 6.82 (s, 1H), 4.31 (q, J = 7.0 Hz, 2H), 3.82 (s, 1H), 1.33 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.4, 161.1, 159.2, 135.3, 134.2, 114.2, 112.4, 102.2, 95.5, 83.6, 74.2, 61.6, 55.3, H Et p-clc 6 H 4 (Z)-Ethyl 7-(4-chlorophenyl)-2-diazo-3-hydroxy-5-oxohept-3-en-6-ynoate (1f). 3 Yellow solid (172 mg, 54%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 7.47 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 6.86 (s, 1H), 4.31 (q, J = 7.0 Hz, 2H), 1.35 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.8, 160.6, 158.2, 136.4, 133.6, 128.9, 119.0, 102.9, 93.1, 85.0, 74.5, 61.7, 14.2.

17 H Et p-fc 6 H 4 (Z)-Ethyl 2-diazo-7-(4-fluorophenyl)-3-hydroxy-5-oxohept-3-en-6-ynoate (1g). 3 Yellow solid (169 mg, 56%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 7.54 (dd, J = 9.0, 5.5 Hz, 2H), 7.06 (dd, J = 9.0, 9.0 Hz, 2H), 6.85 (s, 1H), 4.31 (q, J = 7.0 Hz, 2H), 1.34 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.7, 164.6, 162.6, 160.7, 158.5, (d, J = 8.50 Hz, 1C), (d, J = Hz, 1C), 102.7, 93.4, 84.1, 74.4, 61.7, H Ph Ph (Z)-2-Diazo-3-hydroxy-1,7-diphenylhept-3-en-6-yne-1,5-dione (1h). 3 Yellow solid (177 mg, 56%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 7.65 (d, J = 7.5 Hz, 2H), (m, 3H), 7.50 (t, J = 7.5 Hz, 2H), 7.42 (t, J = 7.5 Hz, 1H), 7.37 (t, J = 7.5 Hz, 2H), 6.94 (s, 1H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.6, 159.4, 137.0, 133.1, 132.7, 132.4, 130.2, 128.9, 128.5, 127.3, 120.5, 103.7, 95.1, 84.2, H Ph p-mec 6 H 4 (Z)-2-Diazo-3-hydroxy-1-phenyl-7-p-tolylhept-3-en-6-yne-1,5-dione (1i). 3 Yellow solid (201 mg, 61%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 7.65 (d, J = 7.5 Hz, 2H), 7.58 (t, J = 7.5 Hz, 1H), 7.49 (t, J = 7.5 Hz, 2H), 7.45 (d, J = 7.5 Hz, 2H), 7.18 (d, J = 7.5 Hz, 2H), 6.93 (s, 1H), 2.37 (s, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.8, 184.6, 159.7, 140.8, 137.0, 133.2, 132.4, 129.3, 128.9, 127.3, 117.5, 103.5, 95.7, 83.9, 82.0, H Ph p-n-prc 6 H 4 (Z)-2-Diazo-3-hydroxy-1-phenyl-7-(4-propylphenyl)hept-3-en-6-yne-1,5-dione

18 (1j). 3 Yellow solid (222 mg, 62%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 7.66 (d, J = 7.5 Hz, 2H), 7.59 (t, J = 7.5 Hz, 1H), (m, 4H), 7.18 (d, J = 7.5 Hz, 2H), 6.92 (s, 1H), 2.61 (t, J = 7.5 Hz, 2H), (m, 2H), 0.94 (t, J = 7.5 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.8, 159.8, 145.6, 137.1, 132.7, , 128.9, 128.7, 127.4, 117.6, 103.6, 95.8, 83.9, 82.1, 56.7, 38.0, 24.2, H Ph p-mec 6 H 4 (Z)-2-Diazo-3-hydroxy-7-(4-methoxyphenyl)-1-phenylhept-3-en-6-yne-1,5-dione (1k). 3 Yellow solid (187 mg, 54%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 7.64 (d, J = 7.5 Hz, 2H), 7.57 (t, J = 7.5 Hz, 1H), (m, 4H), 6.89 (s, 1H), 6.87 (d, J = 7.5 Hz, 2H), 3.81 (s, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.7, 184.5, 156.0, 137.0, 135.3, 134.3, 132.6, 128.8, 127.3, 114.2, 112.3, 103.2, 96.0, 83.7, 82.0, H Ph p-clc 6 H 4 (Z)-7-(4-Chlorophenyl)-2-diazo-3-hydroxy-1-phenylhept-3-en-6-yne-1,5-dione (1l). 3 Yellow solid (175 mg, 50%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), (m, 2H), (m, 1H), (m, 4H), (m, 2H), 6.94 (s, 1H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 185.1, 184.7, 156.0, 137.0, 136.6, 133.7, 132.8, 129.1, 129.0, 127.4, 119.0, 103.9, 93.7, 85.0, H Ph p-fc 6 H 4 (Z)-2-Diazo-7-(4-fluorophenyl)-3-hydroxy-1-phenylhept-3-en-6-yne-1,5-dione (1m). 3 Yellow solid (164 mg, 49%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 7.65 (d, J = 7.5 Hz, 2H), (m, 3H), 7.50 (t, J = 7.5 Hz, 2H), 7.07 (t, J = 8.5 Hz, 2H), 6.94 (s, 1H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 185.0, 164.6, 162.6, 159.2, 137.0, (d, J = 8.5 Hz), 132.8, 128.9, 127.4, 115.9,

19 103.7, 94.0, 84.0, 82.2, H p-mec 6 H 4 Bn N (S,Z)-1-(4-Benzyl-2-oxooxazolidin-3-yl)-2-diazo-3-hydroxy-7-p-tolylhept-3-en-6-y ne-1,5-dione (1n). 3 Yellow solid (124 mg, 29%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 7.47 (dd, J = 18.5, 8.5 Hz, 2H), (m, 2H), (m, 1H), (m, 4H), (m, 1H), 4.35 (t, J = 8.5 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), 2.38 (s, 1H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.4, 159.3, 159.2, 152.6, 140.8, 134.4, 132.4, 129.3, 129.2, 129.0, 127.6, 117.4, 103.0, 95.6, 83.8, 78.3, 67.1, 55.5, 37.4, IR (KBr): 3095, 2958, 2867, 2220, 2108, 1714, 1643, 1569, 1382, 1266, 1075, 851, 739 cm -1. HR-MS calcd for [M] + : C 24 H 19 N 3 5 : , found: H Ph Et (4Z,8E)-Ethyl 2-diazo-5-hydroxy-3-oxo-9-phenylnona-4,8-dien-6-ynoate (1o). Yellow solid (186 mg, 60%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 7.42 (d, J = 8.0 Hz, 2H), (m, 3H), 7.17 (d, J = 15.0 Hz, 1H), 6.81 (s, 1H), 6.28 (d, J = 15.0 Hz, 1H), 4.31 (q, J = 7.5 Hz, 2H), 1.33 (t, J = 7.5 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.5, 160.6, 158.5, 146.0, 135.2, 129.7, 128.8, 126.7, 105.6, 102.6, 94.4, 86.2, 65.5, IR (KBr): 2981, 1716, 1646, 1558, 1418, 1313, 1217, 1082, 1047, 812, 750, 690 cm -1. MS (EI) m/z: 310 (M + ), 282, 210, 199, 149, 115, 57, 43. HRMS calcd for [M] + C 17 H 14 4 : , found: H Et CH 3 (CH 2 ) 6 (4Z,8E)-Ethyl 2-diazo-5-hydroxy-3-oxohexadeca-4,8-dien-6-ynoate (1p). Yellow liquid (179 mg, 54%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 6.72 (s, 1H), (m, 1H), 5.62 (dt, J = 15.0, 7.0 Hz, 1H), 4.29 (q, J = 7.0 Hz, 1H), 4.09 (s, 1H), 2.15 (m, 2H), 1.40 (q, J = 7.0 Hz, 2H), 1.31 (t, J = 7.0 Hz, 3H), 1.27 (m, 8H),

20 0.86 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm ) δ 184.5, 160.7, 159.0, 153.8, 151.0, 107.8, 102.3, 94.2, 82.9, 61.5, 33.4, 31.7, 29.0, 28.9, 28.3, 22.6, 14.2, IR(KBr): 2927, 2855, 2110, 1717, 1637,1309, 1136, 1068, 694 cm -1. MS (EI) m/z: 332, 304, 279, 260, 235, 219, 191, 177, 149, 111, 91, 84, 57, 43. HRMS calcd for [M] + C 18 H 24 4 : , found: H Et (Z)-Ethyl 2-diazo-5-hydroxy-9-methyl-3-oxodeca-4,8-dien-6-ynoate (1q). Yellow liquid (131 mg, 50%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 6.70 (s, 1H), 5.42 (s, 1H), 4.29 (q, J = 7.5 Hz, 2H), 4.10 (s, 1H), 1.96 (s, 3H), 1.87 (s, 3H), 1.31 (t, J = 7.5 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.4, 160.8, 159.6, 155.9, 102.0, 93.9, 86.8, 61.6, 30.6, 25.3, 21.7, IR (KBr): 2980, 2114, 1716, 1646, 1558, 1384, 1189, 1050, 864, 694, 566 cm -1. MS (EI) m/z: 262, 241, 223, 205, 191, 167, 149, 129, 107, 85, 71, 57, 43. HRMS calcd for [M] + C 13 H 14 4 : , found: H Et S (Z)-Ethyl 2-diazo-5-hydroxy-3-oxo-7-(thiophen-3-yl)hept-4-en-6-ynoate (1r). 3 Yellow solid (154 mg, 53%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 7.68 (d, J = 2.0 Hz, 1H), 7.32 (dd, J = 5.0, 2.0 Hz, 1H), 7.21 (d, J = 5.0 Hz, 1H), 6.85 (s, 1H), 4.32 (q, J = 7.0 Hz, 2H), 1.35 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm ) δ 184.7, 160.7, 158.8, 132.4, 129.9, 126.0, 119.9, 102.6, 90.0, 84.1, 61.7, H Et (Z)-Ethyl 7-cyclopropyl-2-diazo-3-hydroxy-5-oxohept-3-en-6-ynoate (1s). 3 Yellow solid (107 mg, 43%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H),

21 6.62 (s, 1H), 4.26 (q, J = 7.0 Hz, 2H), (m, 1H), 1.30 (t, J = 7.0 Hz, 3H), (m, 4H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.3, 160.6, 159.4, 101.7, 101.1, , 61.5, 14.2, 9.2, 0.0. H n-bu Et (Z)-Ethyl 2-diazo-3-hydroxy-5-oxoundec-3-en-6-ynoate (1t). 3 Yellow liquid (156 mg, 59%). 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 6.69 (s, 1H), 4.30 (q, J = 7.0 Hz, 2H), 2.38 (q, J = 7.0 Hz, 2H), (m, 2H), (m, 2H), 1.33 (t, J = 7.0 Hz, 3H), 0.92 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.7, 160.8, 159.4, 102.1, 96.3, 80.4, 76.4, 61.6, 29.8, 22.0, 19.0, 14.3, H n-bu Ph (Z)-2-Diazo-3-hydroxy-1-phenylundec-3-en-6-yne-1,5-dione (1u). 3 Yellow solid (118 mg, 40%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), (m, 2H), (m, 1H), 7.48 (t, J = 8.0 Hz, 2H), 6.73 (s, 1H), 2.39 (t, J = 7.0 Hz, 2H), (m, 2H), (m, 2H), 0.91 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.8, 184.7, 160.0, 137.1, 132.7, 128.9, 127.4, 103.1, 98.4, 82.0, 76.3, 29.7, 21.9, 19.0, H Me 3 Si Et (Z)-Ethyl 2-diazo-5-hydroxy-3-oxo-7-(trimethylsilyl)hept-4-en-6-ynoate (1v). Yellow solid (137 mg, 49%), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (s, 1H), 6.77 (s, 1H), 4.30 (q, J = 7.0 Hz, 2H), 1.33 (t, J = 7.0 Hz, 3H), 0.23 (s, 9H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 185.1, 160.6, 157.5, 102.9, 101.8, 98.4, 74.5, 61.2, 14.2, IR (KBr): 3121, 2962, 2896, 2195, 2140, 1711, 1576, 1417, 1307, 1066, 942, cm -1. MS (EI) 280 (M + ), 252, 238, 219, 209, 191, 167, 151, 97, 71(100), 67, 43. HRMS calcd for [M] + C 12 H 16 4 Si: , found:

22 2. General procedure for regioselective synthesis of -pyrones 2 (Method A) and 3(2H)-furanones 3 (Method B) Method A for synthesis of -pyrones 2: A mixture of substrate 1a (0.2 mmol, 57 mg) in MeH (4 ml) was stirred in the presence of AgSbF 6 (10 mol %) at 25 o C for 5 minutes. The reaction mixture was concentrated in vacuum, and the residue was purified by flash chromatography to yield 2a (R 1 = Et, R 2 = Ph) as a white solid (55 mg) in 95% yield and 3a (R 1 = Et, R 2 = Ph) as a white solid (1.7 mg) in 3% yield. Method B for synthesis of 3(2H)-furanones 3: A solution of substrate 1a (0.2 mmol, 57 mg) in DCE was syringed into a stirring mixture of Et 3 N (0.2 mmol) and AgAc (10 mol%) in DCE (4 ml) at 25 o C for 1 hour. After stirred for another one hour, the reaction mixture concentrated in vacuum, and the residue was purified by flash chromatography to yield 3a (R 1 = Et, R 2 = Ph) as a white solid (49 mg) in 86.4% yield and 2a (R 1 = Et, R 2 = Ph) as a white solid (1.5 mg) in 2.6% yield. Et Ethyl 2-diazo-2-(4-oxo-6-phenyl-4H-pyran-2-yl)acetate (2a). Yellow solid (Method A, 56 mg, 98%, 2a/3a = 97:3), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (m, 2H), (m, 3H), 6.97 (d, J = 2.0 Hz, 1H), 6.66 (d, J = 2.0 Hz, 1H), 6.32 (s, 1H), 4.37 (q, J = 7.0 Hz, 3H), 1.36 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 178.2, 161.5, 161.4, 153.2, 131.4, 131.1, 130.8, 129.2, 128.9, 125.5, 110.8, 62.2, IR (KBr): 2925, 2851, 2108, 1714, 1640, 1553, 1387, 1262, 1138, 735, 682. MS (EI) 284 (M + ), 256, 228, 184, 171, 156, 128, 118, 102(100), 90, 77, 69, 53. HRMS calcd for [M] + C 15 H 12 4 : , found: Et (Z)-Ethyl 2-(5-benzylidene-4-oxo-4,5-dihydrofuran-2-yl)-2-diazoacetate (3a).

23 Yellow solid (Method B, 51 mg, 89%, 2a/3a = 3:97), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.65 (dd, J = 3.5, 1.5 Hz, 2H), (m, 3H), 6.72 (s, 1H), 6.32 (s, 1H), 4.38 (q, J = 7.0 Hz, 2H), 1.37 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.7, 166.7, 160.8, 145.0, 131.7, 131.1, 129.8, 128.9, 125.9, 111.7, 103.9, 62.6, IR (KBr): 2925, 2847, 2104, 1718, 1685, 1652, 1561, 1387, 1175, 1042, 785, 686. MS (EI) 284 (M + ), 256, 211, 199, 156,143, 118(100), 102, 90, 53. HRMS calcd for [M] + C 15 H 12 4 : , found: Et Ethyl 2-diazo-2-(4-oxo-6-p-tolyl-4H-pyran-2-yl)acetate (2b). Yellow solid (Method A, 58 mg, 98%, 2b/3b = 99:1), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.53 (d, J = 8.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 6.96 (d, J = 2.0 Hz, 1H), 6.63 (d, J = 2.0 Hz, 1H), 4.38 (q, J = 7.0 Hz, 2H), 2.42 (s, 3H), 1.37 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 206.9, 184.7, 166.3, 160.9, 144.6, 140.4, 131.1, 129.7, 128.9, 111.9, 103.9, 62.5, 30.8, IR (KBr): 2925, 2855, 2100, 1702, 1644, 1511, 1382, 1266, 1150, 1076, 839, 740. MS (EI) 298 (M + ), 270, 242, 213, 198, 185, 170, 142, 119, 116(100), 91, 69, 53, 41. HRMS calcd for [M] + C 16 H 14 4 : , found: Et (Z)-Ethyl 2-diazo-2-(5-(4-methylbenzylidene)-4-oxo-4,5-dihydrofuran-2-yl)acetate (3b). Yellow solid (Method B, 57 mg, 95%, 2b/3b = 6:94), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.54 (d, J = 8.0 Hz, 2H), 7.22 (d, J =8.0 Hz, 2H), 6.70 (s, 1H), 6.31 (s, 1H), 4.38 (q, J = 7.0 Hz, 2H), 2.37 (s, 3H), 1.37 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 206.9, 161.7, 161.4, 152.9, 142.0, 129.9, 128.0, 125.4,

24 110.8, 110.1, 62.1, 30.9, 21.4, IR (KBr): 2929, 2851, 2108, 1714, 1652, 1557, 1370, 1179, 1030, 897, 818, 744. MS (EI) 298 (M + ), 272, 257, 211, 170, 132(100), 104, 93, 78, 51, 40. HRMS calcd for [M] + C 16 H 14 4 : , found: Et n-pr Ethyl 2-diazo-2-(4-oxo-6-(4-propylphenyl)-4H-pyran-2-yl)acetate (2c). Yellow solid (Method A, 63 mg, 97%, 2c/3c = 98:2), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.53 (d, J = 8.5 Hz, 2H), 7.27 (d, J = 8.5 Hz, 2H), 6.94 (d, J = 2.0 Hz, 1H), 6.61 (d, J = 2.0 Hz, 1H), 4.36 (q, J = 7.0 Hz, 2H), 2.63 (t, J = 7.5 Hz, 2H), (m, 2H), 1.35 (t, J = 7.0 Hz, 3H), 0.94 (t, J = 7.5 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 178.2, 161.8, 161.4, 152.9, 146.7, 129.3, 128.2, 125.5, 110.8, 110.2, 64.5, 62.1, 37.8, 24.1, 14.3, IR (KBr): 2925, 2867, 2108, 1706, 1652, 1577, 1387, 1270, 1154, 1071, 860, 735. MS (EI) 326 (M + ), 298, 269, 241, 226, 213, 197, 169, 144, 128, 115(100), 91, 59, 53, 41. HRMS calcd for [M] + C 18 H 18 4 : , found: Et Pr-n (Z)-Ethyl 2-diazo-2-(4-oxo-5-(4-propylbenzylidene)-4,5-dihydrofuran-2-yl)acetate (3c). Yellow solid (Method B, 61 mg, 94%, 2c/3c = 6:94), mp H-NMR (500 MHz, CDCl 3, ppm) δ 7.54 (d, J = 8.0 Hz, 2H), 7.20 (d, J = 8.0 Hz, 2H), 6.69 (s, 1H), 6.29 (s, 1H), 4.36 (q, J = 7.0 Hz, 2H), 2.58 (t, J = 7.0 Hz, 2H), (m, 2H), 1.35 (t, J = 7.0 Hz, 3H), 0.92 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.6, 166.3, 160.9, 145.2, 144.7, 131.1, 129.2, , 112.0, 111.9, 103.9, 62.5, 37.9, 24.1, 14.2, IR (KBr): 2963, 2867, 2112, 1710, 1644, 1569, 1374, 1275, 1171, 1026, 901, 794, 740. MS (EI) 326 (M + ), 300, 271, 241, 211, 160, 143, 131(100),

25 115, 103, 77, 53, 43. HRMS calcd for [M] + C 18 H 18 4 : , found: t-bu Et t-bu Ethyl 2-(6-(3,5-di-tert-butylphenyl)-4-oxo-4H-pyran-2-yl)-2-diazoacetate (2d). yellow solid (Method A, 78 mg, 98%, 2d/3d = 100:0), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.57 (m, 1H), 7.48 (d, J = 1.7 Hz, 2H), 6.97 (d, J = 2.1 Hz, 1H), 6.69 (d, J = 2.1 Hz, 1H), 4.38 (q, J = 7.0 Hz, 2H), 1.36 (t, J = 7.0 Hz, 3H), 1.34 (s, 18H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 178.4, 162.4, 161.4, 153.0, 151.9, 130.1, 125.8, 119.9, 110.8, 110.5, 62.1, 35.0, 31.2, IR (KBr): 3049, 2960, 2867, 2117, 1716, 1644, 1573, 1386, 1269, 1046, 929, 880, 742, cm -1. MS (EI) m/z: 396 (M + ), 325, 296, 253, 199, 155, 115, 83, 57, 40. HRMS calcd for [M] + C 23 H 28 4 : , found: Et t-bu Bu-t (Z)-Ethyl 2-(5-(3,5-di-tert-butylbenzylidene)-4-oxo-4,5-dihydrofuran-2-yl)-2-diazoacetate (3d). Yellow solid (Method B, 78 mg, 98%, 2d/3d = 0:100), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.56 (s, 2H), 7.47 (s, 1H), 6.78 (s, 1H), 6.35 (s, 1H), 4.40 (q, J = 7.0 Hz, 2H), 1.37 (t, J = 7.0 Hz, 3H), 1.34 (s, 18H). 13 C-NMR (125.8 MHz, CDCl 3, ppm ) δ 184.8, 166.2, 160.9, 151.4, 144.8, 131.0, 125.5, 124.6, 113.2, 104.2, 62.5, 34.8, 31.3, IR (KBr): 3047, 2951, 2867, 2125, 1730, , 1577, 1368, 1185, 1046, 804 cm -1. MS (EI) m/z: 396 (M + ), 370, 313, 267, 230, 187, 155, 128, 92, 57, 40. HRMS calcd for [M] + C 23 H 28 4 : , found:

26 Et Me Ethyl 2-diazo-2-(6-(4-methoxyphenyl)-4-oxo-4H-pyran-2-yl)acetate (2e). Yellow solid (Method A, 61 mg, 97%, 2e/3e = 96:4), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.60 (d, J = 9.0 Hz, 2H), 6.91 (d, J = 9.0 Hz, 2H), 6.69 (d, J = 2.0 Hz, 1H), 6.30 (d, J = 2.0 Hz, 1H), 4.37 (q, J = 7.0 Hz, 2H), 3.83 (s, 3H), 1.36 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 178.3, 162.2, 161.6, 161.5, , 123.1, 114.6, 110.7, 109.3, 64.6, 62.1, 55.5, IR (KBr): 2921, 2847, 2108, 1714, 1698, 1644, 1503, 1457, 1374, 1250, 1188, 1030, 835, 735. MS (EI) 314 (M + ), 288, 258, 242, 214, 199, 186, 158, 148(100),132, 120, 77, 69, 51, 40. HRMS calcd for [M] + C 16 H 14 5 : , found: Et CH 3 (Z)-Ethyl2-diazo-2-(5-(4-methoxybenzylidene)-4-oxo-4,5-dihydrofuran-2-yl)aceta te (3e). Yellow solid (Method B, 60 mg, 95%, 2e/3e = 5:95), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.56 (d, J = 9.0 Hz, 2H), 6.97 (d, J = 9.0 Hz, 2H), 6.92 (s, 1H), 6.56 (s, 1H), 4.36 (q, J = 7.0 Hz, 2H), 3.85 (s, 1H), 1.37 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.5, , 161.0, 160.9, 144.0, 132.9, 124.3, 114.4, 111.9, 104.0, 62.5, 55.3, IR (KBr): 2934, 2847, 2117, 1718, 1648, 1557, 1507, 1457, 1254, 1167, 1071, 835, 794, 740. MS (EI) 314 (M + ), 288, 242, 211, 158, 148(100), 133, 120, 91, 51, 43. HRMS calcd for [M] + C 16 H 14 5 : , found: Et Cl

27 Ethyl 2-(6-(4-chlorophenyl)-4-oxo-4H-pyran-2-yl)-2-diazoacetate (2f). Yellow solid (Method A, 62 mg, 98%, 2f/3f = 94:6), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.57 (d, J = 8.5 Hz, 2H), 7.47 (d, J = 8.5 Hz, 2H), 6.97 (d, J = 2.0 Hz, 1H), 6.64 (d, J = 2.0 Hz, 1H), 4.38 (q, J = 7.0 Hz, 2H), 1.36 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 177.9, 161.3, 160.5, 153.3, 137.7, 129.5, 129.3, 126.8, 110.9, 103.9, 64.4, 62.2, IR (KBr): 2925, 2851, 2104, 1698, 1644, 1533, 1490, 1382, 1258, 1163, 1076, 1022, 847, 740. MS (EI) 318 (M + ), 290, 262, 233, 218, 190, 152, 136(100), 126, 111, 101, 89, 69, 53, 44. HRMS calcd for [M] + C 15 H 11 Cl 4 : , found: Et Cl (Z)-Ethyl 2-(5-(4-chlorobenzylidene)-4-oxo-4,5-dihydrofuran-2-yl)-2-diazoacetate (3f). Yellow solid (Method B, 56 mg, 88%, 2f/3f = 1:99), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.58 (d, J = 9.0 Hz, 2H), 7.38 (d, J = 9.0 Hz, 2H), 6.66 (s, 1H), 6.32 (s, 1H), 4.39 (q, J = 7.0 Hz, 2H), 1.37 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.5, 166.9, 161.3, 160.8, 145.1, 135.9, 132.2, 130.3, 129.3, 110.4, 103.9, 62.7, IR (KBr): 2921, 2855, 2104, 1698, 1648, 1553, 1399, 1175, 1022, 831, 735. MS (EI) 318 (M + ), 291, 273, 245, 227, 199, 164, 152(100), 124, 89, 63,,53, 43. HRMS calcd for [M] + C 15 H 11 Cl 4 : , found: Et F Ethyl 2-diazo-2-(6-(4-fluorophenyl)-4-oxo-4H-pyran-2-yl)acetate (2g). Yellow solid (Method A, 57 mg, 95%, 2g/3g = 96:4), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.63 (dd, J = 8.5, 5.0 Hz, 2H), 7.17 (dd, J = 8.5, 8.5 Hz, 2H), 6.95 (d, J = 2.0 Hz, 1H), 6.95 (d, J = 2.0 Hz, 1H), 4.37 (q, J = 7.0 Hz, 2H), 1.35 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 177.9, 165.5, 163.5, (d, J = 77.5

28 Hz), 133.1, 127.8, (d, J = 8.75 Hz), (d, J = Hz), (d, J = 15.5 Hz), 104.0, 62.2, IR (KBr): 2921, 2855, 2092, 1702, 1511, 1387, 1275, 1175, 1071, 852, 740. MS (EI) 302 (M + ), 284, 246, 217, 202, 174, 146, 136, 120(100), 108, 95, 75, 69, 53, 40. HRMS calcd for [M] + C 15 H 11 F 4 : , found: Et F (Z)-Ethyl 2-diazo-2-(5-(4-fluorobenzylidene)-4-oxo-4,5-dihydrofuran-2-yl)acetate (3g). Yellow solid (Method B, 56 mg, 92%, 2g/3g = 2:98), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.66 (dd, J = 8.5, 5.5 Hz, 2H), 7.11 (dd, J = 8.5, 8.5 Hz, 2H), 6.69 (s, 1H), 6.33 (s, 1H), 4.39 (q, J = 7.0 Hz, 2H), 1.38 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.5, 166.6, 164.3, 162.3, 160.8, 144.7, (d, J = 8.5 Hz), (d, J = 3.38 Hz), (d, J = 21.75), 110.5, 103.9, 62.6, IR (KBr): 2925, 2855, 2108, 1718, 1590, 1503, 1374, 1217, 1175, 1030, 827, 735. MS (EI) 302 (M + ), 284, 246, 217, 189, 146, 136(100), 108, 93, 69, 53, 43. HRMS calcd for [M] + C 15 H 11 F 4 : , found: (1-Diazo-2-oxo-2-phenylethyl)-6-phenyl-4H-pyran-4-one (2h). Yellow solid (Method A, 60 mg, 95%, 2h/3h = 98:2), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.66 (d, J = 7.5 Hz, 2H), 7.57 (t, J = 7.5 Hz, 1H), 7.53 (d, J = 7.5 Hz, 2H), 7.48 (t, J = 7.5 Hz, 3H), 7.44 (t, J = 7.5 Hz, 2H), 7.06 (d, J = 2.0 Hz, 1H), 6.68 (d, J = 2.0 Hz, 1H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 185.1, 178.3, 161.9, 153.3, 136.6, 132.7, 131.4, 130.6, 129.1, 128.9, 127.4, 125.5, 112.5, 111.0, IR (KBr): 3054, 3021, 2104, 1644, 1598, 1445, 1395, 1262, 1167, 1080, 922, 760, 682 cm -1. MS (EI) 316 (M + ), 288, 232, 203, 178, 155, 142, 127, 105, 102(100), 77, 69, 44, 39. HRMS calcd for [M] + C 19 H 12 3 : , found:

29 (Z)-2-Benzylidene-5-(1-diazo-2-oxo-2-phenylethyl)furan-3(2H)-one (3h). Yellow solid (Method B, 60 mg, 95%, 2h/3h = 4:96), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (m, 2H), (m, 3H), 7.52 (t, J = 7.5 Hz, 2H), (m, 3H), 6.75 (s, 1H), 6.34 (s, 1H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 185.0, 184.6, 166.8, 144.6, 136.1, 133.1, 131.7, 131.2, 130.0, 129.0, 128.9, 127.4, 112.2, 105.1, IR (KBr): 3149, 3058, 2925, 2108, 1689, 1644, 1548, 1362, 1291, 1171, 1026, 943, 798, 686 cm -1. MS (EI) 316 (M + ), 287, 259, 231, 203, 170, 130, 118(100), 90, 77, 63, 49, 39. HRMS calcd for [M] + C 19 H 12 3 : , found: (1-Diazo-2-oxo-2-phenylethyl)-6-p-tolyl-4H-pyran-4-one (2i). Yellow solid (Method A, 62 mg, 94%, 2i/3i = 98:2), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.67 (d, J = 7.5 Hz, 2H), (m, 1H), 7.49 (t, J = 7.5 Hz, 2H), 7.42 (d, J = 8.0 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2H), 7.04 (d, J = 2.0 Hz, 1H), 6.66 (d, J = 2.0 Hz, 1H), 2.40 (s, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 185.2, 178.4, 162.2, 153.1, 142.1, 136.7, 132.7, 129.8, 128.9, 127.9, 127.4, 125.5, 112.6, 110.4, 72.3, IR (KBr): 3195, 3116, 3066, 3025, 2108, 1644, 1602, 1569, 1387, 1254, 1175, 1042, 935, 814, 711 cm -1. HRMS calcd for [M] + C 20 H 14 3 : , found: (Z)-5-(1-Diazo-2-oxo-2-phenylethyl)-2-(4-methylbenzylidene)furan-3(2H)-one (3i).

30 Yellow solid (Method B, 64 mg, 97%, 2i/3i = 7:93), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.68 (d, J = 7.5 Hz, 2H), 7.62 (t, J = 7.5 Hz, 1H), (m, 4H), 7.20 (d, J = 8.0 Hz, 2H), 6.73 (s, 1H), 6.33 (s, 1H), 2.37 (s, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 185.0, 184.7, 166.4, 144.3, 140.6, 136.2, 133.0, 131.2, 129.7, 129.0, 128.9, 127.4, 112.4, 105.2, 72.0, IR (KBr): 3153, 3033, 2917, 2851, 2112, 1694, 1644, 1553, 1370, 1175, 1030, 935, 810, 706 cm -1. HRMS calcd for [M] + C 20 H 14 3 : , found: n-pr 2-(1-Diazo-2-oxo-2-phenylethyl)-6-(4-propylphenyl)-4H-pyran-4-one (2j). Yellow solid (Method A, 67 mg, 93%, 2j/3j = 98:2), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.66 (d, J = 7.5 Hz, 2H), 7.56 (t, J = 7.5 Hz, 1H), (m, 4H), 7.23 (d, J = 8.0 Hz, 2H), 7.05 (d, J = 1.5 Hz, 1H), 6.65 (d, J = 1.5 Hz, 1H), 2.61 (t, J = 7.5 Hz, 2H), (m, 2H), 0.93 (t, J = 7.5 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 185.2, 178.3, 162.1, 153.0, 146.8, 136.6, 132.7, 129.2, 129.0, 128.0, 127.4, 125.4, 112.4, 110.3, 72.3, 37.7, 24.1, IR (KBr): 3049, 2937, 2854, 2108, 1635, 1593, 1390, 1261, 1166, 942, 851, 714, 656 cm -1. HRMS calcd for [M] + C 22 H 18 3 : , found: Pr-n (Z)-5-(1-Diazo-2-oxo-2-phenylethyl)-2-(4-propylbenzylidene)furan-3(2H)-one (3j). Yellow solid (Method B, 69 mg, 96%, 2j/3j = 6:94), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.68 (d, J = 8.0 Hz, 2H), 7.63 (t, J = 7.0 Hz, 1H), (m, 4H), 7.21 (d, J = 8.0 Hz, 2H), 6.75 (s, 1H), 6.34 (s, 1H), 2.59 (q, J = 7.5 Hz, 2H), (m, 2H), 0.94 (t, J = 7.5 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 185.0, 184.7, 166.4, 145.4, 144.3, 136.2, 133.0, 131.3, 129.2, , 127.4,

31 112.6, 105.2, 72.0, 37.9, 24.2, IR (KBr) cm -1 : 3062, 2921, 2858, 2112, 1685, 1635, 1552, 1378, 1166, 938, 706, 660 cm -1. MS (EI) 358 (M + ), 329, 304, 261, 147, 131, 105(100), 91, 77, 51, 44. HRMS calcd for [M] + C 22 H 18 3 : , found: Me 2-(1-Diazo-2-oxo-2-phenylethyl)-6-(4-methoxyphenyl)-4H-pyran-4-one (2k). Yellow solid (Method A, 65 mg, 94%, 2k/3k = 98:2), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.66 (d, J = 7.5 Hz, 2H), 7.57 (t, J = 7.5 Hz, 1H), 7.49 (d, J = 7.5 Hz, 2H), 7.46 (d, J = 9.0 Hz, 2H), 7.00 (d, J = 2.0 Hz, 1H), 6.93 (d, J = 9.0 Hz, 2H), 6.58 (d, J = 2.0 Hz, 1H), 3.84 (s, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 185.2, 178.3, 162.2, 162.0, 152.9, 136.7, 132.7, 129.0, 127.4, 127.2, 122.9, 114.5, 112.4, 109.5, 72.2, IR (KBr): 3158, 3058, 2929, 2838, 2104, 1644, 1594, 1503, 1374, 1171, 1026, 835, 698 cm -1. HRMS calcd for [M] + C 20 H 14 4 : , found: Me (Z)-5-(1-Diazo-2-oxo-2-phenylethyl)-2-(4-methoxybenzylidene)furan-3(2H)-one (3k). Yellow solid (Method B, 66 mg, 96%, 2k/3k = 5:95), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.66 (d, J = 7.5 Hz, 2H), 7.60 (t, J = 7.5 Hz, 1H), 7.58 (d, J = 8.5 Hz, 2H), 7.51 (t, J = 7.5 Hz, 2H), 6.90 (d, J = 8.5 Hz, 2H), 6.70 (s, 1H), 6.31 (s, 1H), 3.83 (s, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.8, 184.7, 165.8, 161.0, 143.7, 136.2, 133.0, 133.0, 129.0, 127.4, 124.3, 114.5, 112.4, 105.3, 71.9, IR (KBr): 3153, 3054, 2925, 2834, 2104, 1681, 1631, 1590, 1366, 1246, 1026, 939, 823, 706 cm -1. HRMS calcd for [M] + C 20 H 14 4 : , found:

32 Cl 2-(4-Chlorophenyl)-6-(1-diazo-2-oxo-2-phenylethyl)-4H-pyran-4-one (2l). Yellow solid (Method A, 68 mg, 97%, 2l/3l = 96:4), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (m, 2H), (m, 1H), (m, 2H), (m, 2H), (m, 2H), 7.04 (d, J = 2.0 Hz, 1H), 6.68 (d, J = 2.0 Hz, 1H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 185.1, 178.1, 160.9, 153.4, 137.8, 136.6, 132.8, 129.5, 129.2, 129.0, 127.5, 126.5, 112.5, 111.2, IR (KBr): 3187, 3066, 2929, 2838, 2100, 1652, 1594, 1382, 1258, 1088, 930, 831, 702 cm -1. HRMS calcd for [M] + C 19 H 11 Cl 3 : , found: Cl (Z)-2-(4-Chlorobenzylidene)-5-(1-diazo-2-oxo-2-phenylethyl)furan-3(2H)-one (3l). Yellow solid (Method B, 67 mg, 96%, 2l/3l = 3:97), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (m, 2H), (m, 1H), (m, 4H), (m, 2H), 6.68 (s, 1H), 6.35 (s, 1H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.8, 184.5, 166.9, 144.8, 136.1, 136.0, 133.2, 132.2, 130.2, 129.2, 129.0, 127.5, 110.7, 105.0, IR (KBr): 3153, 3050, 2921, 2847, 2108, 1689, 1635, 1565, 1370, 1291, 1088, 939, 814, 694 cm -1. HRMS calcd for [M] + C 19 H 11 Cl 3 : , found: F 2-(1-Diazo-2-oxo-2-phenylethyl)-6-(4-fluorophenyl)-4H-pyran-4-one (2m). Yellow solid (Method A, 65 mg, 97%, 2m/3m = 94:6), mp o C. 1 H-NMR (500

33 MHz, CDCl 3, ppm) δ 7.65 (d, J = 7.0 Hz, 2H), 7.56 (t, J = 7.0 Hz, 1H), (m, 4H), 7.12 (t, J = 8.5 Hz, 2H), 7.04 (d, J = 1.5 Hz, 1H), 6.64 (d, J = 1.5 Hz, 1H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 185.1, 178.2, 165.4, 163.4, 161.0, 153.3, 136.5, 132.7, (d, J = 8.5 Hz), (d, J = 8.88 Hz), (d, J = 5.25 Hz), (d, J = 22.0 Hz), 112.3, 110.7, IR (KBr): 3058, 2925, 2120, 1647, 1597, 1560, 1510, 1382, 1232, 1162, 917, 830, 710, 656 cm -1. HRMS calcd for [M] + C 19 H 11 F 3 : , found: F (Z)-5-(1-Diazo-2-oxo-2-phenylethyl)-2-(4-fluorobenzylidene)furan-3(2H)-one (3m). Yellow solid (Method B, 63 mg, 95%, 2m/3m = 3:97), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.68 (d, J = 7.5 Hz, 2H), (m, 3H), 7.51 (t, J = 7.5 Hz, 2H), 7.06 (t, J = 8.5 Hz, 2H), 6.67 (s, 1H), 6.33 (s, 1H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.8, 184.5, 166.8, 164.3, 162.3, (d, J = 2.50 Hz), 136.0, (d, J = 8.13 Hz), 129.0, (d, J = 3.38 Hz), 127.4, (d, J = Hz), 110.9, 104.9, IR (KBr): 3053, 2929, 2120, 1680, 1635, 1556, 1369, 1232, 1154, 938, 776, 660 cm -1. HRMS calcd for [M] + C 19 H 11 F 3 : , found: Bn N 4-Benzyl-3-(2-diazo-2-(4-oxo-6-p-tolyl-4H-pyran-2-yl)acetyl)oxazolidin-2-one (2n). Yellow solid (Method A, 84 mg, 98%, 2n/3n = 98:2), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.52 (d, J = 8.5 Hz, 2H), 7.34 (t, J = 8.5 Hz, 2H), (m, 3H), 7.18 (d, J = 7.5 Hz, 2H), 7.00 (d, J = 2.0 Hz, 1H), 6.64 (d, J = 2.0 Hz, 1H), (m, 1H), 4.37 (t, J = 8.5 Hz, 1H), 4.21 (dd, J = 8.5, 7.5 Hz, 1H), 3.30 (dd, J

34 = 13.5, 3.5 Hz, 1H), 2.90 (dd, J = 13.5, 8.5 Hz, 1H), 2.41 (s, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 178.2, 162.0, 159.8, 152.6, 142.1, 140.6, 134.3, 129.8, 129.2, 129.0, 127.9, 127.6, 125.5, 111.7, 110.4, 69.1, 67.2, 55.4, 37.4, IR (KBr): 3062, 2921, 2842, 2125, 1776, 1644, 1374, 1212, 939, 818, 698 cm -1. HRMS calcd for [M] + C 24 H 19 N 3 5 : , found: Bn N (Z)-4-Benzyl-3-(2-diazo-2-(5-(4-methylbenzylidene)-4-oxo-4,5-dihydrofuran-2-yl) acetyl)oxazolidin-2-one (3n). Yellow solid (Method B, 83 mg, 97%, 2n/3n = 2:98), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ 7.56 (d, J = 8.0 Hz, 2H), (m, 2H), (m, 1H), 7.23 (d, J = 8.0 Hz, 2H), 7.19 (d, J = 8.0 Hz, 2H), (m, 1H), 4.39 (t, J = 8.5 Hz, 1H), 4.24 (dd, J = 9.0, 7.0 Hz, 1H), 3.33 (dd, J = 13.5, 3.5 Hz, 1H), 2.91 (dd, J = 13.5, 8.5 Hz, 1H), 2.38 (s, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 184.9, 166.3, 159.1, 152.7, 144.4, 140.6, 134.3, 131.3, 129.7, 129.2, 129.1, 128.9, 127.6, 112.4, 105.0, 68.2, 67.4, 55.6, 37.4, IR (KBr): 3149, 3029, 2921, 2847, 1776, 1685, 1644, 1565, 1374, 1212, 1105, 1030, 918, 810, 698 cm -1. HRMS calcd for [M] + C 24 H 19 N 3 5 : , found: Et (E)-Ethyl 2-diazo-2-(4-oxo-6-styryl-4H-pyran-2-yl)acetate (2o). Yellow solid (Method A, 57 mg, 92%, 2o/3o = 97:3), mp o C. 1 H-NMR (500 MHz, CDCl 3, ppm) δ (m, 5H), 7.08 (d, J = 16.0 Hz, 1H), 6.89 (s, 1H), 6.62 (d, J = 16.0 Hz, 1H), 6.16 (s, 1H), 4.34 (q, J = 7.0 Hz, 2H), 1.34 (t, J = 7.0 Hz, 3H). 13 C-NMR (125.8 MHz, CDCl 3, ppm) δ 178.1, 161.3, 159.7, 152.5, 135.9, 134.5, 129.8, 128.9, 127.4, 119.1, 113.4, 110.7, 64.5, 62.0, IR(KBr): 2981, 2112, 1716, 1702, 1652, 1392, 1377, 1217, 1177, 1068, 962, 752 cm -1. MS (EI) m/z: 310 (M + ), 282, 253, 225,