Yield:885267-36-7 69.4%

Reaction Conditions:

with Dess-Martin periodane in dichloromethane at 0 - 20; for 14 h;

Steps:

319.A Part A: 6-bromo-3-fluoropicolinaldehyde
To a solution of (6-bromo-3-fluoropyridin-2-yl)methanol (4 g, 19.42 mmol) in DCM (80 mL) cooled to 0 °C was added Dess-Martin periodinane (12.35 g, 29.1 mmol). The mixture was warmed to room temperature and stirred for 14 h. The reaction mixture was quenched with saturated aqueous sodium bicarobonate (50 mL) and diluted with DCM (100 mL). The mixture was filtered through diatomaceous earth (Celite). The bed was washed with DCM (100 mL) and the filtrate was transferred to a separating funnel. The aqueous layer was discarded and the organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure to afford 6-bromo-3-fluoropicolinaldehyde (5.5 g, 27.0 mmol, 69.4 % yield) as a colorless oil. NMR (400 MHz, CDCh): δ 10.09 (s, 1H), 7.71 (dd, J= 8.8, 3.6 Hz, 1H), 7.50 - 7.46 (m, 1H).

References:

BRISTOL-MYERS SQUIBB COMPANY;BRONSON, Joanne J.;CHEN, Ling;DITTA, Jonathan L.;DZIERBA, Carolyn Diane;JALAGAM, Prasada Rao;LUO, Guanglin;MACOR, John E.;MAISHAL, Tarun Kumar;NARA, Susheel Jethanand;RAJAMANI, Ramkumar;SISTLA, Ramesh Kumar;THANGAVEL, Soodamani WO2017/59085, 2017, A1 Location in patent:Page/Page column 328; 329

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