Macrocycles Derived from Cinchona Alkaloids: A Thermodynamic vs Kinetic Study

Stuart J. Rowan; Jeremy K M Sanders

Macrocycles Derived from Cinchona Alkaloids: A Thermodynamic vs Kinetic Study

Stuart J. Rowan, Jeremy K M Sanders^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

69 Citations (Scopus)

Abstract

Cyclization of the quinine-derived monomer (2a): HO-Cq-OMe, under thermodynamic control, gives mainly cyclic trimer Cq₃ (7a), whereas kinetic cyclization of the similar monomer HO-Cq-OH (8) gives a mixture of cyclic products. This difference in product distribution is attributed to predisposition of the monomer unit, which means the building block adopts a more stable conformation in cyclic trimer than it can in cyclic tetramer. The reversibility of the thermodynamic reaction was demonstrated using electrospray mass spectrometry to monitor the catalyzed mixing of the two cyclic trimers Cq₃ (7a) and Cc₃ (7b), which results in the statistically expected 1:3:3:1 ratio of all possible cyclic trimers Cc₃:Cc₂Cq:CcCq₂:Cq₃.

Original language	English
Pages (from-to)	1536-1546
Number of pages	11
Journal	Journal of Organic Chemistry
Volume	63
Issue number	5
Publication status	Published - 1998 Mar 6
Externally published	Yes

ASJC Scopus subject areas

Organic Chemistry

Cite this

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title = "Macrocycles Derived from Cinchona Alkaloids: A Thermodynamic vs Kinetic Study",

abstract = "Cyclization of the quinine-derived monomer (2a): HO-Cq-OMe, under thermodynamic control, gives mainly cyclic trimer Cq3 (7a), whereas kinetic cyclization of the similar monomer HO-Cq-OH (8) gives a mixture of cyclic products. This difference in product distribution is attributed to predisposition of the monomer unit, which means the building block adopts a more stable conformation in cyclic trimer than it can in cyclic tetramer. The reversibility of the thermodynamic reaction was demonstrated using electrospray mass spectrometry to monitor the catalyzed mixing of the two cyclic trimers Cq3 (7a) and Cc3 (7b), which results in the statistically expected 1:3:3:1 ratio of all possible cyclic trimers Cc3:Cc2Cq:CcCq2:Cq3.",

author = "Rowan, {Stuart J.} and Sanders, {Jeremy K M}",

year = "1998",

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language = "English",

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journal = "Journal of Organic Chemistry",

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T1 - Macrocycles Derived from Cinchona Alkaloids

T2 - A Thermodynamic vs Kinetic Study

AU - Rowan, Stuart J.

AU - Sanders, Jeremy K M

PY - 1998/3/6

Y1 - 1998/3/6

N2 - Cyclization of the quinine-derived monomer (2a): HO-Cq-OMe, under thermodynamic control, gives mainly cyclic trimer Cq3 (7a), whereas kinetic cyclization of the similar monomer HO-Cq-OH (8) gives a mixture of cyclic products. This difference in product distribution is attributed to predisposition of the monomer unit, which means the building block adopts a more stable conformation in cyclic trimer than it can in cyclic tetramer. The reversibility of the thermodynamic reaction was demonstrated using electrospray mass spectrometry to monitor the catalyzed mixing of the two cyclic trimers Cq3 (7a) and Cc3 (7b), which results in the statistically expected 1:3:3:1 ratio of all possible cyclic trimers Cc3:Cc2Cq:CcCq2:Cq3.

AB - Cyclization of the quinine-derived monomer (2a): HO-Cq-OMe, under thermodynamic control, gives mainly cyclic trimer Cq3 (7a), whereas kinetic cyclization of the similar monomer HO-Cq-OH (8) gives a mixture of cyclic products. This difference in product distribution is attributed to predisposition of the monomer unit, which means the building block adopts a more stable conformation in cyclic trimer than it can in cyclic tetramer. The reversibility of the thermodynamic reaction was demonstrated using electrospray mass spectrometry to monitor the catalyzed mixing of the two cyclic trimers Cq3 (7a) and Cc3 (7b), which results in the statistically expected 1:3:3:1 ratio of all possible cyclic trimers Cc3:Cc2Cq:CcCq2:Cq3.

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Macrocycles Derived from Cinchona Alkaloids: A Thermodynamic vs Kinetic Study

Abstract

ASJC Scopus subject areas

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