Hydride → 4-Pyridin-3-yl-but-3-enoic acid

HRID 337190Notes

Reaction equation

HRID 337190 reaction equation
[H-].C[C@H]1C[C@]23[C@@H]4CCCN2CCC[C@@H]3C(=O)C[C@@H]4C1.[N:20]1[CH:25]=[CH:24][CH:23]=[C:22]([CH:26]=[CH:27][CH2:28][C:29]([O:31]CC)=[O:30])[CH:21]=1>>[N:20]1[CH:25]=[CH:24][CH:23]=[C:22]([CH:26]=[CH:27][CH2:28][C:29]([OH:31])=[O:30])[CH:21]=1

Participants

4

Reactant 3

HCID 166653HydrideHCID 5462445LycopodineHCID 68953529HCID 68953529, compound

Product 1

HCID 4394-Pyridin-3-yl-but-3-enoic acid

Procedure

The target compound 4-pyridin-3-yl-but-3-enoic acid (Compound 2035) was prepared by two steps starting from the commercial available 3-Pyridinecarboxaldehyde. Reaction of this aldehyde with ethyl acrylate and triphenylphosphine in a sealed tube for 4 hr at 140° C. gave ethyl 4-pyridin-3-yl-3-butenoate in a 55% yield. Kirby, Anthony J.; Walwyn, David R. Effective molarities for intramolecular hydride transfer. Reduction by 1,4-dihydropyridines of the neighboring α-ketoester group. Gazzetta Chimica Italiana (1987), 117(11), 667-80. This reaction is a self-priming Wittig reaction and the yield was not optimized. Gilbert Stork, R. A. Kretchmer, R. H. Schlessinger. The Stereospecific Total Synthesis of dl-Lycopodine. J. Am. Chem. Soc. (1968), 90, 1647. Hydrolysis of the ester using the routine condition and the subsequent purification with preparative HPLC afforded the target compound 2035 with almost quantitative yield.

Workup

  1. customa self-priming Wittig reaction
  2. customthe subsequent purification with preparative HPLC

Sources & evidence

ORD record
ord-5da25ed0147d4b5ea6f3b6d73f84f745
Source dataset
uspto-grants-2014_11
Patent number
US08889720B2

Reaction notes

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