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A kinetic approach to the mechanism of cationic polyolefinic cyclization. Simple and extended π-participation
Croatica Chemica Acta, 67 (1994), 2; 171-188. urn:nbn:hr:163:546870
Borčić, Stanko; Kronja, Olga; Humski, Krešimir

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Borčić, S., Kronja, O. & Humski, K. (1994). A kinetic approach to the mechanism of cationic polyolefinic cyclization. Simple and extended π-participation. Croatica Chemica Acta, 67. (2), 171-188. Retrieved from https://urn.nsk.hr/urn:nbn:hr:163:546870

Borčić, Stanko, et al. "A kinetic approach to the mechanism of cationic polyolefinic cyclization. Simple and extended π-participation." Croatica Chemica Acta, vol. 67, no. 2, 1994, pp. 171-188. https://urn.nsk.hr/urn:nbn:hr:163:546870

Borčić, Stanko, Olga Kronja and Krešimir Humski. "A kinetic approach to the mechanism of cationic polyolefinic cyclization. Simple and extended π-participation." Croatica Chemica Acta 67, no. 2 (1994): 171-188. https://urn.nsk.hr/urn:nbn:hr:163:546870

Borčić, S., Kronja, O. and Humski, K. (1994) 'A kinetic approach to the mechanism of cationic polyolefinic cyclization. Simple and extended π-participation', Croatica Chemica Acta, 67(2), pp. 171-188. Available at: https://urn.nsk.hr/urn:nbn:hr:163:546870 (Accessed 25 November 2024)

Borčić S, Kronja O, Humski K. A kinetic approach to the mechanism of cationic polyolefinic cyclization. Simple and extended π-participation. Croatica Chemica Acta [Internet]. 1994 [cited 2024 November 25];67(2):171-188. Available at: https://urn.nsk.hr/urn:nbn:hr:163:546870

S. Borčić, O. Kronja and K. Humski, "A kinetic approach to the mechanism of cationic polyolefinic cyclization. Simple and extended π-participation", Croatica Chemica Acta, vol. 67, no. 2, pp. 171-188, 1994. [Online]. Available at: https://urn.nsk.hr/urn:nbn:hr:163:546870. [Accessed: 25 November 2024]

Metadata
Title (english)A kinetic approach to the mechanism of cationic polyolefinic cyclization. Simple and extended π-participation
AuthorStanko Borčić
AuthorOlga Kronja
AuthorKrešimir Humski
Author's institutionUniversity of Zagreb
Faculty of Pharmacy and Biochemistry
(Department of organic chemistry)
Scientific / art field,
discipline and subdiscipline		NATURAL SCIENCES
Chemistry
Organic Chemistry
Abstract (english)
This review deals with the mechanism of the biomimetic olefinic cationic polycyclizations considering relative rate effects, activation parameters, substituent rate effects, a, p correlation and secondary deuterium kinetic isotope effects (KIE) in solvolysis, obtained with tertiary and benzylic substrates comprising one, two or more double bonds, respectively, sited at the same positions as in the natural precursor (C-5, C-9, C-13). Kinetic behaviour of substrates with one double bond at position 5 (models for mono- cyclization) which are structurally related to structures 16U and 22U suggests that the formation of the first cyclohexane ring is a concerted process with some exceptions (16U with p-OCH3). In solvolysis of chlorides with double bonds at positions 5 and 9 (28 and 29U) extended it-parcipation occurs, i.e. both double bonds of the aliphatic chain are involved in the rate determining step. Substrastes with more then two double bonds (30U and 31U) solvolyze by way of extended 7i-participation. It remains unclear if two or three double bonds are involved. The paper also shows clear evidence that the magnitude of 3-deuterium secondary KIE are the most sensitive probe for neighboring group participation.
Languageenglish
Publication typeOther - Other
Publication statusPublished
Peer reviewPeer review
Publication versionPublished version
Journal titleCroatica Chemica Acta
Numberingvol. 67, no. 2, pp. 171-188
p-ISSN0011-1643
e-ISSN1334-417X
URN:NBNurn:nbn:hr:163:546870
Publication1994
Document URLhttps://hrcak.srce.hr/136883
Type of resourceText
Access conditionsOpen access
Terms of useLicence In copyright icon
Created on2020-04-29 15:05:21