TY  - JOUR
AU  - Lorenc, Ljubinka
AU  - Gašić, Miroslav J.
AU  - Juranić, Ivan
AU  - Dabović, Milan
AU  - Minailović, M. Lj.
PY  - 1980
UR  - https://cer.ihtm.bg.ac.rs/handle/123456789/2709
AB  - Kinetic measurements of the solvolysis of (Z)-3α- and (Z)-3β-, and (E)-3α- and (E)-3β-tosyloxy-5,10-secocholest-1(10)-en-5-ones in buffered aqueous acetone (90 : 10 v/v) reveal that the (Z)-3α-, (E)-3α-, and (E)-3β-tosylates are solvolysed according to a first-order rate law (the relative rates being ca. 1 : 3 : 8), while the (Z)-3β-ester, under the same conditions, reacts at a much slower rate by a complex mechanism, the kinetics of which are best approximated by a second-order law. These data and product analysis indicate that the former three esters are solvolysed with considerable double bond participation [resulting in the case of the (E)-3-esters in intramolecular cyclopropane ring closure], and that this interaction is unimportant for the (Z)-3β-tosylate. On the basis of conformational analysis of the starting tosylates and stereoelectronic requirements for homoallylic interaction, a possible mechanistic pathway for these solvolyses is proposed.
PB  - Royal Society of Chemistry
T2  - Journal of the Chemical Society, Perkin Transactions 2
T1  - Synthesis, structure, and reactions of secosteroids containing a medium-sized ring. Part 17. Structure-reactivity relationship in the solvolysis of 5,10-secosteroidal 3-tosylates
IS  - 9
SP  - 1356
EP  - 1365
UR  - https://hdl.handle.net/21.15107/rcub_cer_2709
ER  - 

@article{
author = "Lorenc, Ljubinka and Gašić, Miroslav J. and Juranić, Ivan and Dabović, Milan and Minailović, M. Lj.",
year = "1980",
abstract = "Kinetic measurements of the solvolysis of (Z)-3α- and (Z)-3β-, and (E)-3α- and (E)-3β-tosyloxy-5,10-secocholest-1(10)-en-5-ones in buffered aqueous acetone (90 : 10 v/v) reveal that the (Z)-3α-, (E)-3α-, and (E)-3β-tosylates are solvolysed according to a first-order rate law (the relative rates being ca. 1 : 3 : 8), while the (Z)-3β-ester, under the same conditions, reacts at a much slower rate by a complex mechanism, the kinetics of which are best approximated by a second-order law. These data and product analysis indicate that the former three esters are solvolysed with considerable double bond participation [resulting in the case of the (E)-3-esters in intramolecular cyclopropane ring closure], and that this interaction is unimportant for the (Z)-3β-tosylate. On the basis of conformational analysis of the starting tosylates and stereoelectronic requirements for homoallylic interaction, a possible mechanistic pathway for these solvolyses is proposed.",
publisher = "Royal Society of Chemistry",
journal = "Journal of the Chemical Society, Perkin Transactions 2",
title = "Synthesis, structure, and reactions of secosteroids containing a medium-sized ring. Part 17. Structure-reactivity relationship in the solvolysis of 5,10-secosteroidal 3-tosylates",
number = "9",
pages = "1356-1365",
url = "https://hdl.handle.net/21.15107/rcub_cer_2709"
}

Lorenc, L., Gašić, M. J., Juranić, I., Dabović, M.,& Minailović, M. Lj.. (1980). Synthesis, structure, and reactions of secosteroids containing a medium-sized ring. Part 17. Structure-reactivity relationship in the solvolysis of 5,10-secosteroidal 3-tosylates. in Journal of the Chemical Society, Perkin Transactions 2
Royal Society of Chemistry.(9), 1356-1365.
https://hdl.handle.net/21.15107/rcub_cer_2709

Lorenc L, Gašić MJ, Juranić I, Dabović M, Minailović ML. Synthesis, structure, and reactions of secosteroids containing a medium-sized ring. Part 17. Structure-reactivity relationship in the solvolysis of 5,10-secosteroidal 3-tosylates. in Journal of the Chemical Society, Perkin Transactions 2. 1980;(9):1356-1365.
https://hdl.handle.net/21.15107/rcub_cer_2709 .

Lorenc, Ljubinka, Gašić, Miroslav J., Juranić, Ivan, Dabović, Milan, Minailović, M. Lj., "Synthesis, structure, and reactions of secosteroids containing a medium-sized ring. Part 17. Structure-reactivity relationship in the solvolysis of 5,10-secosteroidal 3-tosylates" in Journal of the Chemical Society, Perkin Transactions 2, no. 9 (1980):1356-1365,
https://hdl.handle.net/21.15107/rcub_cer_2709 .