A new and convenient preparation of 1-aminocyclopropanecarboxylic acid from acrolein

Salaün, Jacques; Marguerite, J.; Karkour, B.

doi:10.1021/jo00301a013

Cited by 37 publications

(11 citation statements)

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“…However, although the nitrile and carboxylate groups have comparable ability to stabilize an adjacent ~a r b a n i o n ,~ the cyclization of 2-N-benzyl-4-chlorobutyronitrile (36,37) and of (3R)-llc were unfortunately not achieved under a variety of basic conditions (i.e., K2C03 and Cs2C03 in DMF at 80°C, KOH in DMSO, K-t-BuO in THF, n-BuLi, NaH in THF, ...) (37). As we had previously reported the quantitative ready cyclization of a 4-chloro-2-iminobutyronitrile under smooth basic conditions (i.e., K2C03 in DMF at room temperature, for instance (11,36)), we undertook the transformation of the benzylamine l l c into the corresponding imine. First of all, we tried to cleave the N-benzyl protecting group; curiously, in spite of many attempts under various hydrogenolysis conditions (i.e., either with 5-10% Pd/C catalysis under 1-53 psi (1 psi = 6.9 kPa) hydrogen pressure (38), with a stoechiometric amount of Pd/C and ammonium formiate as hydrogen source (39), or with 20% of the Pearlman catalyst (40) (Pd(OH)2) under 1-53 psi hydrogen pressure), the amine deprotection of l l c and of its chlorohydrate derivative, prepared by bubbling gaseous HCl through an etheral solution of l l c , failed.…”

Section: Omcrique a Partir De L'acttate De 2-(hydroxymcthyl)butyle (mentioning

confidence: 99%

Total asymmetric syntheses of (1S,2S)-norcoronamic acid, and of (1R,2R)- and (1S,2S)-coronamic acids from the diastereoselective cyclization of 2-(N-benzylideneamino)-4-chlorobutyronitriles

Gaucher¹,

Ollivier²,

Marguerite³

et al. 1994

Can. J. Chem.

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(3R)-2-(N-Benzylideneamino)-4-chloro-3-methylbutyronitrile 3, prepared from the commercially available methyl (2S)-3-hydroxy-2-methyl propionate 5 (96% ee), readily underwent potassium carbonate induced cyclization to provide, after acid hydrolysis (6 N HCl) and chromatography, the (1S,2S)-norcoronamic acid 1a with 88% diastereoselectivity and > 95% enantiomeric excess. From (2R)-2-(hydroxymethyl)butyl acetate 23 (> 88% ee) obtained by enzymatic enantioselective hydrolysis with lipase PS, was prepared the (3S)-2-(N-benzylideneamino)-3-(chloromethyl)valeronitrile 29, which after base-induced cyclization (K2CO3) and acid (6 N HCl) or basic (0.8 N NaOH) hydrolysis led to the non-natural (1R,2R)-coronamic acid 18 (> 88% ee). Also from this same acetate (2R)-23 was prepared the (3R)-3-(chloromethyl)-2-[(diphenylmethylene)amino]pentanenitrile 37, which provided the (1S,2S)-coronamic acid 17 (> 88% ee) after base-induced cyclization (K2CO3 or LDA) and acid hydrolysis (6 N HCl). It is noteworthy that these short synthetic sequences, which do not require any expensive chiral auxiliary or optically active precursors, do not alter the enantiomeric purity of the stereogenic centers of these 2,3-methanoamino acids. However, the E diastereoselectivity of these cyclizations was not improved by using bulky N-(diphenylmethylene)amino substituent, contrary to results of some molecular mechanic calculations (MAD).

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Section: Omcrique a Partir De L'acttate De 2-(hydroxymcthyl)butyle (mentioning

confidence: 99%

Total asymmetric syntheses of (1S,2S)-norcoronamic acid, and of (1R,2R)- and (1S,2S)-coronamic acids from the diastereoselective cyclization of 2-(N-benzylideneamino)-4-chlorobutyronitriles

Gaucher¹,

Ollivier²,

Marguerite³

et al. 1994

Can. J. Chem.

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“…95-97 °C. 1 1-Bromocyclopropanecarbonitrile (5). A solution of the 1-bromocyclopropanecarbonylamide 4 (108.5 g, 0.67 mol) in dry CH 3 CN (400 mL) was dehydrated over P 2 O 5 (187.5 g, 1.34 mol) for 5 h at 80 °C.…”

Section: Methodsmentioning

confidence: 99%

“…55-58 °C / 2 mmHg) to afford 1-bromocyclopropanecarbonitrile 5 (81.5 g, 85% yield) as a colourless oil. 1 …”

Section: Journal Of Chemical Research 2014 419mentioning

confidence: 99%

“…1,2 Compounds containing a cyclopropane ring have been attracting attention as pharmaceutical intermediates. The physiological importance of cyclopropane-containing compounds has led to various synthetic methods for these three-membered rings.…”

mentioning

confidence: 99%

“…An increasing number of therapeutic agents, including antiarrhythmic, antipsychotic, and antitumour compounds, have structures which incorporate a cyclopropane ring. 1,2 Compounds containing a cyclopropane ring have been attracting attention as pharmaceutical intermediates. The physiological importance of cyclopropane-containing compounds has led to various synthetic methods for these three-membered rings.…”

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confidence: 99%

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