Stereoselective synthesis of 3-alkylated glutamic acids: application to the synthesis of secokainic acid

Jako, Isabelle; Uiber, Pierre; Mann, André; Wermuth, Camille G.; Boulanger, Thierry; Norberg, Bernadette; Evrard, G.; Durant, François

doi:10.1021/jo00019a055

Cited by 55 publications

(23 citation statements)

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“…Highly diastereoselective conjugate addition of lithium divinylcuprate to 5 gave syn product 6 (N-Boc group to vinyl group) exclusively in 88% yield. The observed stereochemical course of this conjugate addition is consistent with a Felkin-Anh model in that the attack on the Re face should take place to afford the observed product [13]. Deprotection of oxazolidine 6 under acidic conditions followed by acetylation gave the key intermediate 7 in 94% overall yield.…”

Section: Synthesis Of 3-pipecolinoglutamic Acid (1)supporting

confidence: 81%

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Application of rhodium-catalyzed cyclohydrocarbonylation to the syntheses of enantiopure homokainoids

Chiou¹,

Schoenfelder

Mann

et al. 2008

Pure and Applied Chemistry

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Kainic acid, rigidified (S)-glutamic acid, is a well-known kainite receptor agonist for the excitatory transmission in the central nerve system. Our interest in highly selective kainite ligands, prompted us to design a series of new kainic homologues, "homokainoids", i.e., conformationally rigidified (S)-glutamic acids. For the syntheses of enantiopure novel homokainoids (pipecolinoglutamic acids), we successfully applied cyclohydrocarbonylation (CHC) reaction that has been developed in these laboratories. Efficient total syntheses of enantiopure novel homokainoids from (R)-serine feature the highly diastereoselective conjugate addition and the regioselective CHC process in the key steps.

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Section: Synthesis Of 3-pipecolinoglutamic Acid (1)supporting

confidence: 81%

“…Our strategy for the syntheses of these homokainates utilizes the diastereoselective conjugate addition [13] to establish the stereochemistry at the C-3 position and the cyclohydrocarbonylation reaction (CHC reaction) to construct the piperidine moiety with proper functional groups [14,15].…”

Section: Introductionmentioning

confidence: 99%

Application of rhodium-catalyzed cyclohydrocarbonylation to the syntheses of enantiopure homokainoids

Chiou¹,

Schoenfelder

Mann

et al. 2008

Pure and Applied Chemistry

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“…In the next step, the TBS protecting group in 9 was removed by exposure to methanolic p -TsOH to give the corresponding alcohol, which was then subjected to reaction with 2,2-dimethoxypropane (2,2-DMP) in the presence of BF 3 ·Et 2 O [24] to produce N , O -acetonide 10 in 93% yield over two steps. For the preparation of the E -isomer of α,β-unsaturated ester 11 , Wittig–Horner reaction employing Garner’s aldehyde has been well known [25–26]; however, we selected stereoselective olefination through deprotonation of 10 with LDA followed by the addition of phenylselenyl bromide [27] and subsequent oxidative elimination of the resulting phenylseleno group with m -CPBA according to our previous report [28], which gave E -isomer 11 in quantitative geometric purity and 90% yield over two steps. Then, the ester moiety of this compound was reduced with DIBAL-H to the corresponding hydroxymethyl functionality to afford 6a in 95% yield [29].…”

Section: Resultsmentioning

confidence: 99%

A new approach toward the total synthesis of (+)-batzellaside B

Wierzejska¹,

Motogoe²,

Makino³

et al. 2012

Beilstein J. Org. Chem.

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SummaryA new synthetic approach to (+)-batzellaside B from naturally abundant L-pyroglutamic acid is presented in this article. The key synthetic step involves Sharpless asymmetric dihydroxylation of an olefinic substrate functionalized with an acetoxy group to introduce two chiral centres diastereoselectively into the structure. Heterocyclic hemiaminal 4, which could be converted from the resulting product, was found to provide stereospecific access to enantiomerically enriched allylated intermediate, offering better prospects for the total synthesis of this natural product.

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“…Our synthesis (Scheme 1) started from the known 9 (R)-cyclohexylideneglyceraldehyde (4), which was easily con-verted into the α,β-unsaturated ester 5. 10 We envisaged that conjugate addition of a suitable nitrogen nucleophile to 5 may prove to be diastereoselctive in view of ample analogous precedence 11 and also our earlier success in a related system. 12 Thus, addition of allylamine to this unsaturated ester in the presence of borax 13 under our developed conditions 12 provided a mixture of two possible isomeric products, syn-and anti-β-amino esters 6 in a combined yield of 88% with a diastereomeric ratio of 82:18 (by 1 H NMR).…”

mentioning

confidence: 98%

Asymmetric Synthesis of d-Proline, d-Pipecolic Acid, (2R,3S,4R)-3,4-Dihydroxyproline, and 1,4-Dideoxy-1,4-imino-d-talitol from a Common Precursor

Chattopadhyay

Mukherjee

2014

Synthesis

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Methodology involving stereoselective aza-Michael addition and ring-closing metathesis as key steps has been developed for the preparation of (2R)-pipecolic acid, (2R)-proline, (2R,3S,4R)-3,4-dihydroxyproline, and the known glycosidase inhibiting azasugar 1,4-dideoxy-1,4-imino-D-talitol from a common starting material namely (R)-cyclohexylideneglyceraldehyde in good overall yields.Naturally occurring azacyclic α-amino acids, such as proline and pipecolic acid, are privileged structures, for example, as a part structure of natural products in either enantiomeric form, 1 in the synthesis of designed peptides, 2 in asymmetric organocatalysis, 3 as building blocks in organic synthesis 4 for the preparation 5 of compounds of type 1 (Figure 1) and catalysts of type 2, etc. Similarly, several hydroxylated proline derivatives of type 3 belonging to the family of azasugars possess useful levels of glycosidase inhibitory activity. 6 As a result numerous methodologies have emerged for the synthesis of these two classes of compounds involving the use of chiral catalysts, chiral-pool material, chiral auxiliaries, etc. 7,8 Although superb catalytic methods are known, and applicable, in principle, for the synthesis of either enantiomer of these important targets, methods involving the simple conversion of readily available materials remain important. Additionally, incorporation of elements of diversity in any such approach would be of further advantage. Herein, we describe a unified approach to Rconfigured two homologous azacyclic amino acids from a common precursor. Figure 1 Azacyclic structures of importanceOur synthesis (Scheme 1) started from the known 9 (R)-cyclohexylideneglyceraldehyde (4), which was easily converted into the α,β-unsaturated ester 5. 10 We envisaged that conjugate addition of a suitable nitrogen nucleophile to 5 may prove to be diastereoselctive in view of ample analogous precedence 11 and also our earlier success in a related system. 12 Thus, addition of allylamine to this unsaturated ester in the presence of borax 13 under our developed conditions 12 provided a mixture of two possible isomeric products, syn-and anti-β-amino esters 6 in a combined yield of 88% with a diastereomeric ratio of 82:18 (by 1 H NMR). The mixture of diastereomers was then reduced with lithium aluminum hydride to obtain the corresponding mixture of primary alcohols 7 which could also not be separated. However, N-protection of this mixture of β-amino alcohols with benzyl chloroformate neatly provided a separable mixture of the corresponding carbamates 8 and 9 in very good yield and in a diastereomeric ratio of ~4:1.Scheme 1 Synthesis of the β-amino alcohols 8 and 9The major product 8 was assigned syn-stereochemistry based on precedence and corroborated by the synthetic work described herein. We surmised that compound 8 could be utilized as a building block in asymmetric synthesis of the projected amino acids if a successful conversion of the primary alcohol function to an olefinic unit N N H HO OH OH OH 1, n = 1, 2 2, n = 1, 2 3 (...

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Stereoselective synthesis of 3-alkylated glutamic acids: application to the synthesis of secokainic acid

Cited by 55 publications

References 1 publication

Application of rhodium-catalyzed cyclohydrocarbonylation to the syntheses of enantiopure homokainoids

Application of rhodium-catalyzed cyclohydrocarbonylation to the syntheses of enantiopure homokainoids

A new approach toward the total synthesis of (+)-batzellaside B

Asymmetric Synthesis of d-Proline, d-Pipecolic Acid, (2R,3S,4R)-3,4-Dihydroxyproline, and 1,4-Dideoxy-1,4-imino-d-talitol from a Common Precursor

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