CC(C)(C)OC(=O)N1CCC[C@@H](N)C1.Clc1ccccn1>CC(C)(C)[O-].Cc1ccccc1.O=C(/C=C/c1ccccc1)/C=C/c1ccccc1.O=C(/C=C/c1ccccc1)/C=C/c1ccccc1.O=C(/C=C/c1ccccc1)/C=C/c1ccccc1.[Na+].[Pd].[Pd].c1ccc(P(c2ccccc2)c2ccc3ccccc3c2-c2c(P(c3ccccc3)c3ccccc3)ccc3ccccc23)cc1>CC(C)(C)OC(=O)N1CCC[C@@H](Nc2ccccn2)C1Vial 1) Pd2(dba)3 (0.018 g, 0.02 mmol) and BINAP (0.024 g, 0.04 mmol) were mixed in toluene (1mL) under N2 and stirred at rt for 5min. Vial 2) sodium tert-butoxide (0.999 g, 10.08 mmol), tert-butyl (R)-3-aminopiperidine-1-carboxylate (1.249 g, 6.05 mmol) and 2-chloropyridine (0.477 mL, 5.04 mmol) were mixed in toluene (6mL) under N2. Added the catalyst solution from vial 1. The mixture was heated at 110°C in an oil-bath. LCMS (3h): product, no SM left. The reaction was cooled to rt and the solvent was evaporated. Added EtOAc, washed with water. Purified by column chromatography (using SP4 TM HPFC system, KP-Sil (50g) column, A=heptane, B=EtOAc/2M NH3 in MeOH (9/1), 27mL/fr, (0% B 2CV, 0-30% B 10CV, 30% B 2CV)) to yield tert-butyl (R)-3-(pyridin-2-ylamino)piperidine-1-carboxylate (1.306 g, 93 %) as yellow solid. [M+H]+ 278. 1H NMR (400 MHz, CDCl3) d 1.42 (s, 9H), 1.51 - 1.64 (m, 2H), 1.68 - 1.8 (m, 1H), 1.93 - 2.05 (m, 1H), 2.81 - 3.36 (m, 2H), 3.45 - 4.16 (m, 3H), 4.50 (d, 1H), 6.42 (d, 1H), 6.5 - 6.62 (m, 1H), 7.36 - 7.45 (m, 1H), 8.02 - 8.13 (m, 1H). Expected Number of Hs: 23 Assigned Hs: 23.
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