Tributylvinyltin → Benzyl 6-[(tert-butoxycarbonyl)amino]-2-methyl-3-vinylbenzoate

HRID 1725912Notes

Reaction equation

Br[C:2]1[C:3]([CH3:26])=[C:4]([C:15]([NH:18][C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])=[CH:16][CH:17]=1)[C:5]([O:7][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=[O:6].[CH2:27]([Sn](CCCC)(CCCC)C=C)[CH2:28]CC>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CN(C=O)C>[C:22]([O:21][C:19]([NH:18][C:15]1[C:4]([C:5]([O:7][CH2:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[O:6])=[C:3]([CH3:26])[C:2]([CH:27]=[CH2:28])=[CH:17][CH:16]=1)=[O:20])([CH3:25])([CH3:24])[CH3:23]

Participants

Conditions

Temperature: 90 °C

Procedure

A mixture of Example 126A (1.4 g, 3.3 mmol), DMF (33 mL) and tributyl(vinyl)tin (1.1 mL, 3.8 mmol) was degassed with argon 30 minutes, treated with Pd(PPh3)4 (577 mg, 0.5 mmol), heated to 90° C. for 18 hours, and concentrated. The concentrate was purified by flash column chromatography on silica gel (200 g) with 50% dichloromethane/hexanes to provide the desired product. MS (ESI(+)) m/e 368 (M+H)+; (ESI(−)) m/e 366 (M−H)−; 1H NMR (300 MHz, DMSO-d6) δ 8.87 (s, 1H), 7.54 (d, 1H), 7.45 (m, 2H), 7.37 (m, 3H), 7.27 (d, 1H), 6.94 (dd, 1H), 5.64 (dd, 1H), 5.31 (dd, 1H), 5.27 (s, 2H), 2.21 (s, 3H), 1.42 (s, 9H).

Workup

concentrationconcentrated
customThe concentrate was purified by flash column chromatography on silica gel (200 g) with 50% dichloromethane/hexanes

Sources & evidence

ORD record: ord-2364f678baa241fd8827121086750f48
Source dataset: uspto-grants-2009_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07491718B2

Reaction notes

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