Stereochemistry of the Bucherer–Bergs and Strecker Reactions of 4-<i>tert</i>-Butylcyclohexanone

Edward, John T.; Jitrangsri, Chote

doi:10.1139/v75-477

Cited by 57 publications

(24 citation statements)

References 10 publications

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“…21 It is generally assumed that alkyl-substituted cycloalkanones form exclusively the α-form of cycloalkanespirohydantoins. 22,23 This is confirmed by the ORTEP structure of spirohydantoin 3d obtained by X-ray analysis (Table 2). Figure 4 shows the X-ray diffraction structures; Table 3 gives the geometry of the intermolecular hydrogen bonds.…”

Section: Resultssupporting

confidence: 71%

Microwave-assisted synthesis of cycloalkanespirohydantoins and piperidylspirohydantoins as precursors of restricted α-amino acids

Rivero¹,

Reynoso²,

Ochoa-Terán³

2011

Arkivoc

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Cycloalkanespirohydantoins 3 and piperidinespirohydantoins 4 were synthesized from cycloalkanones 9 and piperidones 10 under microwave-assisted conditions. Results are compared with those obtained under thermal conditions. Cycloalkanespirohydantoins 3 were N-protected with Boc group and hydrolyzed under basic conditions to obtain five, six and seven-membered ring restricted α-amino acids 12 in very good overall yields (76-94%).

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Section: Resultssupporting

confidence: 71%

Microwave-assisted synthesis of cycloalkanespirohydantoins and piperidylspirohydantoins as precursors of restricted α-amino acids

Rivero¹,

Reynoso²,

Ochoa-Terán³

2011

Arkivoc

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“…11). B reacted with acetic anhydride to give a diacetyl derivative, as would be expected of 5 (11). Under the same conditions, the 40: 60 mixture of A and B from the Bucherer reaction =The same composition of the Bucherer-Bergs product is indicated in its lH nmr spectrum, which shows two peaks for the 1'-hydrogen atom with relative intensities 6:4 (see Table 3); the spectrum of the Strecker product shows only one 1'-hydrogen peak having the same chemical shift as the peak of the major isomer from the Bucherer-Bergs reaction.…”

Section: Resultsmentioning

confidence: 90%

“…from 7. However, 60% of the Bucherer product is also derived from 7, probably reacting via the conformation 7b, and only 40% from 8, probably reacting via the conformation 8a, for reasons discussed earlier (11). It would be expected that the product ratio would be a complicated function of the relative proportions of 7a, 7b, 8a, 8b, and of their relative rates of reaction and of interconversion (the major product probably being formed by the route 7a -, 7b -, hydantoin).…”

Section: Resultsmentioning

confidence: 95%

Stereochemistry of the Bucherer–Bergs and Strecker reactions of tropinone, cis-bicyclo[3.3.0]octan-3-one and cis-3,4-dimethylcyclopentanone

Trigo¹,

Avendaño²,

Santos³

et al. 1979

Can. J. Chem.

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SIN CHEONG WONG. Can. J. Chem. 57,1456 (1979.The tropane-3-spiro-5'-hydantoin (a isomer) obtained from tropinone by the BuchererBergs reaction has been shown by 13C nmr and X-ray diffraction studies to have the 4'-carbonyl group in the equatorial position; the isomer, obtained via the Strecker reaction, has this group axial. The results of these two reactions on cis-bicyclo[3.3.0]octan-3-one and on cis-3,4-dimethylcyclopentanone show, on the basis of the 'H nmr, 13C nmr, and X-ray diffraction studies of the products, a stereochemical course related to the preferred conformation of the cyclopentane rings.

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“…The identity of the a-aminonitrile salts was confirmed by their ir and nmr spectra, and by their conversion into the stable hydantoins when heated with ammonium carbonate (24). The ir spectra of the a-aminonitrile salts did not show a CGN stretching band at 2200 cm-', but were otherwise unexceptional.…”

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confidence: 91%

Preparation of α-aminothioamides from aldehydes

Paventi¹,

Edward²

1987

Can. J. Chem.

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MARTINO PAVENTI and JOHN T. EDWARD. Can. J. Chem. 65, 282 (1987). The conversion of aldehydes into a-aminonitriles and thence into imidazolidin-4-thiones has been studied. Hydrolysis of the appropriate imidazolidin-4-thiones gave thioamides of nine naturally occurring a-amino acids. The possible pre-biotic significance of these compounds is discussed.MARTINO PAVENTI et JOHN T. EDWARD. Can. J. Chem. 65,282 (1987). On a CtudiC la transformation des aldChydes en a-amino-nitriles et Cventuellement en imidazolidinethiones-4. L'hydrolyse des imidazolidinethiones-4 appropriCes conduit aux thioamides de neuf acides a-aminCs naturels. On discute de I'implication prC-biotique possible de ces composts.[Traduit par la revue]In 1953, Miller (1) showed that sparking a mixture of methane, ammonia, hydrogen, and water vapour furnished traces of glycine, alanine, and other common a-amino acids. This historic experiment awakened the interest of many organic chemists in possible pre-biotic routes to proteins, nucleic acids, and polysaccharides on the primitive earth.It seems likely that under the conditions of Miller's experiment aldehydes and hydrogen cyanide are formed (2). These can react with ammonia to give a-aminonitriles 1, which are hydrolysed to a-amino acids-(2). However, the polymerization .of a-amino acids to polypeptides and proteins requires an activation process. Various possible modes of activation that might operate under pre-biotic conditions (heat, cyanamide, adsorption on clays, etc.) have been suggested (2, 3) but are not very plausible.This activation step might have been avoided on the primitive earth if a-aminonitriles had been converted into reactive a-amino acid derivatives rather than into unreactive a-amino acid zwitterions. One such derivative might have been the thioamide. The reactivity of these compounds was demonstrated more than 70 years ago by Johnson and Burnham (4), in the course of their attempts to obtain the thioamide 2 (R' = R~ = H) by treatment of the nitrile 1 (R' = R2 = H) amounts of the cyclic product 4 (R' = R2 = H), all presumably arising from further reaction of the sought-for thioamide 2 (R1 = R 2 = H) (Scheme 1). Later attempts by Gatewood and Johnson (5,6) to obtain other a-aminothioamides by this route gave either no product (6), or products from further reaction of initially formed a-aminothioamides (5, 6). However, Cook et al. (7) obtained 2 (R' = Ph, R2 = H) in 12% yield by treating 1 (R' = Ph, R2 = H) with H2S for 24 h in ether containing a little pyridine.This work indicates a possibility of producing thiopolypeptides and thence polypeptides by the general route of Scheme 1.Consequently, we have prepared a-aminothioamides 2 corresponding to several common a-amino acids a s a preliminary t o searching for conditions to convert them into linear thiopolypeptides.We first required a convenient and general preparation of a-aminonitriles 1. These compounds have long been obtained by the Strecker reaction: ience, NH4Cl and NaCN (= NaCl + NH4CN = NaCl + NH3 + HCN) were used instead...

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Stereochemistry of the Bucherer–Bergs and Strecker Reactions of 4-tert-Butylcyclohexanone

Cited by 57 publications

References 10 publications

Microwave-assisted synthesis of cycloalkanespirohydantoins and piperidylspirohydantoins as precursors of restricted α-amino acids

Microwave-assisted synthesis of cycloalkanespirohydantoins and piperidylspirohydantoins as precursors of restricted α-amino acids

Stereochemistry of the Bucherer–Bergs and Strecker reactions of tropinone, cis-bicyclo[3.3.0]octan-3-one and cis-3,4-dimethylcyclopentanone

Preparation of α-aminothioamides from aldehydes

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