1258431-03-6

Basic information

• Product Name: 2H-Quinolizine-3-carboxylic acid, octahydro-2-oxo-, ethyl ester
• Synonyms: 2H-Quinolizine-3-carboxylic acid, octahydro-2-oxo-, ethyl ester;Ethyl 2-oxooctahydro-1H-quinolizine-3-carboxylate
• CAS NO: 1258431-03-6
• Molecular Formula: C12H19NO3
• Molecular Weight: 225.28416
• Mol File: 1258431-03-6.mol
• Article Data: 3

Chemical Properties

• Boiling Point: 338.5±37.0 °C(Predicted)
• Appearance: /
• Density: 1.14±0.1 g/cm3(Predicted)
• PKA: 11.30±0.20(Predicted)
• CAS DataBase Reference: 2H-Quinolizine-3-carboxylic acid, octahydro-2-oxo-, ethyl ester(CAS DataBase Reference)
• NIST Chemistry Reference: 2H-Quinolizine-3-carboxylic acid, octahydro-2-oxo-, ethyl ester(1258431-03-6)
• EPA Substance Registry System: 2H-Quinolizine-3-carboxylic acid, octahydro-2-oxo-, ethyl ester(1258431-03-6)

Safety Data

• Hazardous Substances Data: 1258431-03-6(Hazardous Substances Data)

Upstream product

• 99392-94-6 1-(2-ethoxycarbonyl)ethyl-2-ethoxycarbonylmethylpiperidine 
• 109-06-8 α-picoline 
• 98202-45-0 ethyl (2E)-7-iodohept-2-enoate 
• 2739-98-2 ethyl 2-(pyridinyl-2)acetate 
• 2739-99-3 2-ethoxycarbonylmethylpiperidine 

Downstream Products

• 475301-86-1 3-methyldecahydro-1H-1,5-methanopyrido[1,2-a][1,5]diazocine 
• 475301-86-1 (1S,5R,11aR)-3-methyldecahydro-1H-1,5-methanopyrido[1,2-a]-[1,5]diazocine 
• 475301-86-1 (+)-sparteine surrogate 

Relevant articles and documents

Revisiting the sparteine surrogate: Development of a resolution route to the (-)-sparteine surrogate

The improved performance of the sparteine surrogate compared to sparteine in a range of applications has highlighted the need to develop an approach to the (-)-sparteine surrogate, previously inaccessible in gram-quantities. A multi-gram scale, chromatography-free synthesis of the racemic sparteine surrogate and its resolution via diastereomeric salt formation with (-)-O,O′-di-p-toluoyl-l-tartaric acid is reported. Resolution on a 10.0 mmol scale gave the diastereomeric salts in 33% yield from which (-)-sparteine surrogate of 937 er was generated. This work solves a key limitation: either enantiomer of the sparteine surrogate can now be readily accessed.

Synthesis of sparteine-like chiral diamines and evaluation in the enantioselective lithiation-substitution of N-(tert-butoxycarbonyl)-pyrrolidine

Three chiral diamines were synthesised and evaluated as sparteine surrogates in the lithiation-substitution of N-(tert-butoxycarbonyl)pyrrolidine. The synthesis and attempted resolution of sparteine-like diamines {(1S*, 2R*, 8R*)-10-methyl-6,10-diazatricyclo [6.3.1.02,6]dodecane and (1S*, 2R*, 9R*)-11-methyl-7,11-diazatricyclo[7.3.1.02,7]tridecane} (via inclusion complex formation) are reported. Unfortunately, it was only possible to resolve the diazatricyclo-[7.3.1.02,7] tridecane compound. An alternative route to (1R,2S,9S)-11-methyl-7,11-diazatricyclo[7.3.1.02.7]tridecane starting from the natural product, (-)-cytisine, is described. This simple three-step route furnished gram-quantities of a (+)-sparteine surrogate. X-ray crystallography of an intermediate in the route, (1R,5S,12S)-3-methoxycarbonyl-decahydro-1,5-methanopyrido [1,2-a][1,5]diazocin-8-one, enabled the stereochemistry of all of the tricyclic diamines described in this paper to be unequivocally established. Two other diamines, starting from (S)-proline and resolved 2-piperidine ethanol, were prepared using standard methods. These diamines lacked the bispidine framework of (-)-sparteine and were found to impart vastly inferior enantioselectivity. It was concluded that, for the asymmetric lithiation-substitution of N-Boc pyrrolidine, a rigid bispidine framework and only three of the four rings of (-)-sparteine are needed for high enantioselectivity. Furthermore, it is shown that diamine (1R,2S,9S)-11-methyl-7,11-diazatricyclo [7.3.1.02,7]tridecane is the first successful (+)-sparteine surrogate.