The Design of Novel<i>N</i>-4‘-Pyridinyl-α-methyl Proline Derivatives as Potent Catalysts for the Kinetic Resolution of Alcohols

Priem, Ghislaine; Pelotier, Béatrice; Macdonald, Simon J. F.; Anson, M.; Campbell, Ian B.

doi:10.1021/jo026485m

Cited by 102 publications

(44 citation statements)

References 35 publications

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“…Researchers at GSK recently described a family of chiral acylating catalysts based on the N-4'-pyridinyla-methylproline structure capable of promoting the kinetic resolution of alcohols with a high level of enantioselectivity. [71] The ready availability of these compounds suggested an exploitation of the presence of their easily functionalizable carboxy function to immobilize these catalysts on different polymer supports. [72] Among others, derivatives 23a-c collected in Figure 9 were prepared connecting N-4'-pyridinyl-amethylproline to low-and high-loading polystyrene (LLPS and HLPS), and to Wang resin by standard condensation methods.…”

Section: -Dimethylaminopyridine Analoguesmentioning

confidence: 99%

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Immobilization of Organic Catalysts: When, Why, and How

2006

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This review article is divided in two parts. In the first part (Sections 2 and 3) selected examples of the publications that appeared in the literature in the period 2003–2005 in the field of immobilized organic catalysis are presented. When appropriate, the results of these publications are compared to those reported earlier and already discussed in a previous review article (see ref. 4). On the basis of this survey, in Section 4 some general considerations about when and why a supported version of an organic catalyst is worth developing are proposed. In Section 4 a list of suggestions about how the process of immobilization should be carried out is also included, taking into account several factors such as the properties of the catalyst, the nature of the support, and the mode of connection of the catalyst to the support.

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Section: -Dimethylaminopyridine Analoguesmentioning

confidence: 99%

“…Extension of the use of catalyst 23b to the kinetic resolution of other secondary alcohols was possible, although the immobilized catalyst performed constantly less efficiently than its best non-supported analogue. [71,73] …”

Section: -Dimethylaminopyridine Analoguesmentioning

confidence: 99%

Immobilization of Organic Catalysts: When, Why, and How

2006

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“…53 The first step of the synthesis is the nucleophilic substitution of 4-chloropyridine with α-methylproline. The carboxylic acid group of the proline can be functionalized by various amines by standard peptide coupling agents (e.g., HATU).…”

Section: Omementioning

confidence: 99%

6.08 Acylation-Type Reactions: Synthesis of Esters via Acyl Transfer

Zell

Schreiner

2014

Comprehensive Organic Synthesis II

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“…[64][65][66] Introduction of an AE-methyl group avoids racemization of the catalysts during their preparation. [65] Scheme 17 Kinetic Resolution of Racemic Alcohols by a Chiral 4-(Pyrrolidin-1-yl)pyridine Racemic N-protected amino alcohols 28, 36, and 37 are also kinetically resolved in the presence of catalyst 35 with high enantioselectivity.…”

Section: Bmentioning

confidence: 99%

Chiral DMAP-Type Catalysts for Acyl-Transfer Reactions

2012

Asymmetric Organocatalysis 1

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Reactivity of DMAP-Type Catalysts4-(Dimethylamino)pyridine (1, DMAP) (Scheme 1) is a valuable and powerful organocatalyst which catalyzes acylation of a wide variety of alcohols. [1][2][3][4][5][6][7][8] In these reactions, 4-(dimethylamino)pyridine works as a nucleophilic catalyst which mediates acyl-transfer reactions from an acyl donor to the substrate via acylpyridinium reactive intermediate 3 (Scheme 2). In 1967, it was found that 4-(dimethylamino)pyridine accelerates the benzoylation of 3-chloroaniline faster than pyridine does by a factor of ca. 10 4 . [9] Independently, the superior activity of 4-(dimethylamino)pyridine as an acylation catalyst was revealed in 1969. [10] It has also been reported that 4-(pyrrolidin-1-yl)pyridine (2, PPY) (Scheme 1) has higher catalytic activity in acylation reactions than 4-(dimethylamino)pyridine. [11] These landmark findings have opened up the chemistry of DMAP-type catalysis. DMAP-catalyzed acyl-transfer reactions have been utilized for O-acylation of alcohol substrates, Nacylation of amine substrates, and C-acylation of enolates and their equivalents. In particular, asymmetric acyl-transfer reactions catalyzed by chiral DMAP-type catalysts have attracted great attention. A wide variety of chiral DMAP-type and PPY-type catalysts have been developed in the last 15 years and the research field on chiral DMAP-catalysis is still rapidly expanding. [12][13][14][15][16][17][18][19][20][21][22][23] Scheme 1 Structure of 4-(Dimethylamino)pyridine and 4-(Pyrrolidin-1yl)pyridine N NMe 2 1 DMAP N N 2 PPYThe currently accepted mechanism of DMAP-catalyzed acylation of alcohols is shown in Scheme 2. Acylpyridinium ion 3 is formed by nucleophilic attack of 4-(dimethylamino)pyridine (1) on an acyl donor. Under the pre-equilibrium between acylpyridinium ion 3 and 4-(dimethylamino)pyridine/acyl donor, acylpyridinium ion 3 undergoes nucleophilic attack by alcohol 4 to give ester 6 and protonated (deactivated) catalyst 7 via transition state 5. Regeneration of the active catalyst 1 usually requires an auxiliary base such as triethylamine. More recently, an efficient acylation process has been reported employing a small amount (0.05-2 mol%) of 4-(dimethylamino)pyridine in the absence of auxiliary bases. [24] 497 for references see p 544This document was downloaded for personal use only. Unauthorized distribution is strictly prohibited.

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The Design of NovelN-4‘-Pyridinyl-α-methyl Proline Derivatives as Potent Catalysts for the Kinetic Resolution of Alcohols

Cited by 102 publications

References 35 publications

Immobilization of Organic Catalysts: When, Why, and How

Immobilization of Organic Catalysts: When, Why, and How

6.08 Acylation-Type Reactions: Synthesis of Esters via Acyl Transfer

Chiral DMAP-Type Catalysts for Acyl-Transfer Reactions

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