Abstract
The mechanism and stereochemical peculiarities of the fragmentation of α-dibromo-derivatives of adamantane by zinc in DMFA were investigated on the example of chiral dibromides. It was shown that the reaction proceeds with the formation of intermediate carbanions; moreover, the formation of a carbanion at the chiral center is accompanied by racemization, and at the bridge carbon atom by transformation of the central chirality of the initial dibromide into the planar chirality of derivatives of 3,7-dimethylenebicyclo[3. 3.1]nonane. This transformation, which obeys definite stereoelectronic requirements, provides for the genetic interrelationship of the configurations of the fragmentable dibromides and fragmentation products.
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Literature cited
J. A. Marshall and J. H. Babler, “A new synthesis of acyclic 1,5-dienes,” Tetrahedron Lett., No. 44, 3861–3864 (1970).
J. H. Babler and A. E. Moorman, “A chromium(II)-promoted heterolytic fragmentation reaction. Application to the synthesis of 1,5-dienes,” J. Org. Chem.,41, No. 8, 1477–1479 (1976).
C. A. Grob, “Mechanismen und Sterochemle der heterolytischen Fragmentierung,” Angew. Chem.,81, No. 15, 8543–8554 (1969).
P. S. Wharton, R. A. Kretchmer, and Y. Sumi, “Trans, trans-2,8-trans-bicyclo[8.4.0]tetradecadlene,” J. Org. Chem.,30, No. 1, 234–237 (1965).
C. A. Grob and W. Baumann, “Die 1,4-Eliminierung unter Fragmentierung,” Helv. Chim. Acta,38, No. 3, 594–610 (1955).
F. N. Stepanov and V. D. Suchoverchov, “Eine neue Fragmentierung in der Adamanteine,” Angew. Chem.,79, No. 19, 860–861 (1967).
F. N. Stepanov, V. D. Sukhoverkhov, V. F. Baklan, and A. G. Yurchenko, “Double fragmentation of the adamantane ring system,” Zh. Org. Khim.,6, No. 4, 884–886 (1970).
W. Fisher and C. A. Grob, “Competing fragmentation, substitution and elimination in the solvolysis of alkylated 3-chloropropanols and their ethers,” Helv. Chim. Acta. 61, No. 7, 2336–2350 (1978).
W. Fisher and C. A. Grob, “Inductive, hyperconjugative and frangometric effects in the solvolysis of 1-substituted 3-bromoadamantanes,” Helv. Chim. Acta,61, No. 5, 1588–1608 (1978).
C. A. Grob, M. Bolleter, and W. Kunz, “Induktive, CC-hyperkonjugative und frangomere Effekte bei solvolytischen Fragmentierungsreaktionen,” Angew. Chem.,92, Np. 9, 734–755 (1980).
R. R. Fraser, M. A. Petit, and J. K. Saunders, “Determination of enantiomeric purity by optically active nuclear magnetic resonance shift reagent of wide applicability,” J. Chem. Soc, Chem. Commun., No. 22, 1450–1451 (1971).
P. A. Krosutskii, I. G. Semenova, and M. I. Novikova, “α-amino acids of the adamantane series. Synthesis and enantiomeric segregation of 1-adamantyl glycine and α-(1-adamantyl)alanine,” Zh. Org. Khim,21., No. 7, 1458–1464 (1985).
P. A. Krasutskii, I. G. Semenova, and A. G. Yurchenko, “Amino acids of the adamantane series. 2. Synthesis and disomeric segregation of adamantyl-1, 3-diglycine. Stereochemistry of the amination of α-bromo acids of adamantane,” Zh. Org. Khim.,21, No. 10, 2057–2062 (1985).
P. A. Krasutskii, V. N. Rodionov, N. S. Chesskaya, and A. G. Yurchenko, “Enantiomeric segregation and absolute configuration of asymmetrical derivatives of 3,6-dimethylene-bicyclo[3.3.1]nonane. Synthesis of chiral derivatives of adamantane,” Zh. Org. Khim., 21., No. 8, 1684–1691 (1985).
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Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 5, pp. 620–623, September–October, 1985.
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Krasutskii, P.A., Chesskaya, N.S., Rodionov, V.N. et al. Mechanism of the fragmentation of the methyl ester of α-bromo-α-(3-bromoadamantyl-1) acetic acid. Theor Exp Chem 21, 593–596 (1985). https://doi.org/10.1007/BF00944101
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DOI: https://doi.org/10.1007/BF00944101