H. Nmr, 400 MHz, CDCl3) ? (ppm) 13.60 (bs, 1H, NH), 7.44-7.17 (m, 5H, H-6, H-7, vol.1

C. Nmr, C-5), 100.6 MHz, CDCl3) ? (ppm) 205.0 (C-2), vol.144, pp.19-20

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, HRMS m/z calcd for C23H40N2O2Si

, After 1 h stirring at the same temperature, the reaction mixture was cooled to -78 °C and a solution of aldehyde (1 equiv) in anhydrous Et2O (4.8 mL/mmol of aldehyde) was added dropwise. After an additional 1 h or 5 h stirring at -78 °C, the reaction mixture was quenched with saturated aqueous NH4Cl and slowly warmed to rt. The aqueous layer was extracted with Et2O (x3). The combined organic layer was washed with brine, dried (Na2SO4), filtered and the filtrate was concentrated under reduced pressure

, to 5:5) to afford the corresponding hydrazones 80 and 81

. Vii, Methyl-side" aldolisation on ?-triisopropylsilyl-?-diazoacetone 2 via boron enolates 1) With chlorodicyclohexylborane

, This solid was dissolved in Et2O (4 mL), and a buffered aqueous solution (pH = 7; 0.3 mL) and hydrogen peroxide (5 µL) were added. The mixture was stirred 3 h between 0 °C and 5 °C. The organic layer was washed with brine (4 mL), dried (MgSO4), filtered and the filtrate was concentrated under reduced pressure. The residue was chromatographed (silica gel neutralized with 2% of NEt3; petroleum ether/ethyl acetate 10:0 to 5:5) to afford the corresponding diazoaldol 3a as a yellow solid. (114 mg; 83% yield). The aldol 3a was, anhydrous Et2O

, With (-)-B-chlorodiisopinocampheylborane

, To a stirred solution of ?-triisopropylsilyl-?-diazoacetone 2 (95 mg; 0.42 mmol) in anhydrous Et2O (3 mL) at -78 °C were added slowly triethylamine (90 µL; 0.63 mmol) and then

, 5 h stirring, a solution of benzaldehyde (51 µL; 0.50 mmol) in anhydrous Et2O (1mL) was added dropwise

, Hydrogen peroxide (30 µL) was added and the mixture was stirred for 10 min between 0 °C and 5 °C. The organic layer was washed with brine (4 mL), dried (MgSO4), filtered and the filtrate was concentrated under reduced pressure. The residue was chromatographed (silica gel neutralized with 2% of NEt3; petroleum ether/ethyl acetate 10:0 to 5:5) to afford the corresponding diazoaldol 3a as a yellow solid (116 mg; 84% yield). The final product was contaminated with traces of diisopinocampheol. The aldol 3a was, After an additional 5 h stirring at -78 °C, the reaction mixture was quenched with a buffered solution

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