Kinetic resolution displaying zeroth order dependence on substrate consumption: Copper-catalyzed asymmetric alcoholysis of azlactones

Makoto Tokunaga; Junya Kiyosu; Yasushi Obora; Yasushi Tsuji

doi:10.1021/ja058112j

Kinetic resolution displaying zeroth order dependence on substrate consumption: Copper-catalyzed asymmetric alcoholysis of azlactones

Makoto Tokunaga, Junya Kiyosu, Yasushi Obora, Yasushi Tsuji

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

29 Citations (Scopus)

Abstract

Kinetic resolution of 4-alkyl-2-aryl-5-oxo-4,5-dihydrooxazole-4-carboxylic acid esters (azlactones 1) were achieved by copper-DTBM-SEGPHOS catalyzed alcoholysis reaction with good selectivity (12 examples). Variation of ee of unreacted substrates 1 and products 2 with conversion was found to follow the theoretical line of zeroth-order kinetic resolution, for which the selectivity profiles and graphical analysis were presented for the first time. The efficiency of resolution in zeroth-order reaction is higher than first-order reaction. For example, the reaction with 1a afforded (S)-1a (99% ee) and (R)-2a (74% ee) at 57% conversion, where the k_rel values were calculated to be 6.7 as zeroth-order kinetic resolution and 37 as first-order kinetic resolution.

Original language	English
Pages (from-to)	4481-4486
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	128
Issue number	13
DOIs	https://doi.org/10.1021/ja058112j
Publication status	Published - Apr 5 2006
Externally published	Yes

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja058112j

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title = "Kinetic resolution displaying zeroth order dependence on substrate consumption: Copper-catalyzed asymmetric alcoholysis of azlactones",

abstract = "Kinetic resolution of 4-alkyl-2-aryl-5-oxo-4,5-dihydrooxazole-4-carboxylic acid esters (azlactones 1) were achieved by copper-DTBM-SEGPHOS catalyzed alcoholysis reaction with good selectivity (12 examples). Variation of ee of unreacted substrates 1 and products 2 with conversion was found to follow the theoretical line of zeroth-order kinetic resolution, for which the selectivity profiles and graphical analysis were presented for the first time. The efficiency of resolution in zeroth-order reaction is higher than first-order reaction. For example, the reaction with 1a afforded (S)-1a (99% ee) and (R)-2a (74% ee) at 57% conversion, where the krel values were calculated to be 6.7 as zeroth-order kinetic resolution and 37 as first-order kinetic resolution.",

author = "Makoto Tokunaga and Junya Kiyosu and Yasushi Obora and Yasushi Tsuji",

year = "2006",

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doi = "10.1021/ja058112j",

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T1 - Kinetic resolution displaying zeroth order dependence on substrate consumption

T2 - Copper-catalyzed asymmetric alcoholysis of azlactones

AU - Tokunaga, Makoto

AU - Kiyosu, Junya

AU - Obora, Yasushi

AU - Tsuji, Yasushi

PY - 2006/4/5

Y1 - 2006/4/5

N2 - Kinetic resolution of 4-alkyl-2-aryl-5-oxo-4,5-dihydrooxazole-4-carboxylic acid esters (azlactones 1) were achieved by copper-DTBM-SEGPHOS catalyzed alcoholysis reaction with good selectivity (12 examples). Variation of ee of unreacted substrates 1 and products 2 with conversion was found to follow the theoretical line of zeroth-order kinetic resolution, for which the selectivity profiles and graphical analysis were presented for the first time. The efficiency of resolution in zeroth-order reaction is higher than first-order reaction. For example, the reaction with 1a afforded (S)-1a (99% ee) and (R)-2a (74% ee) at 57% conversion, where the krel values were calculated to be 6.7 as zeroth-order kinetic resolution and 37 as first-order kinetic resolution.

AB - Kinetic resolution of 4-alkyl-2-aryl-5-oxo-4,5-dihydrooxazole-4-carboxylic acid esters (azlactones 1) were achieved by copper-DTBM-SEGPHOS catalyzed alcoholysis reaction with good selectivity (12 examples). Variation of ee of unreacted substrates 1 and products 2 with conversion was found to follow the theoretical line of zeroth-order kinetic resolution, for which the selectivity profiles and graphical analysis were presented for the first time. The efficiency of resolution in zeroth-order reaction is higher than first-order reaction. For example, the reaction with 1a afforded (S)-1a (99% ee) and (R)-2a (74% ee) at 57% conversion, where the krel values were calculated to be 6.7 as zeroth-order kinetic resolution and 37 as first-order kinetic resolution.

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Kinetic resolution displaying zeroth order dependence on substrate consumption: Copper-catalyzed asymmetric alcoholysis of azlactones

Abstract

All Science Journal Classification (ASJC) codes

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