Synthesis of N-protected α-amino aldehydes from their morpholine amide derivatives

Douat, Céline; Heitz, Annie; Martinez, Jean; Fehrentz, Jean‐Alain

doi:10.1016/s0040-4039(99)01818-3

Cited by 70 publications

(38 citation statements)

References 9 publications

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“…For this purpose, N ‐methoxy‐ N ‐methylamides (the Weinreb amides), that form stabilized tetrahedral five‐membered‐chelate intermediates, have typically been utilized with reactive hydride donors such as lithium aluminum hydride, diisobutylaluminium hydride, and Red‐Al under cryogenic reaction conditions (commonly at < 0 °C) ( Scheme ,a ) . There has also been reported use of tertiary amides having special substituents which reduce the electron‐donating nature of the amide nitrogen onto the carbonyl group, including N ‐acylsultam, N ‐acylsaccharin, N ‐acyl carbazoles and N ‐acylaziridines ( Scheme ,b ) …”

Section: Introductionmentioning

confidence: 99%

Reduction of N,N‐Dimethylcarboxamides to Aldehydes by Sodium Hydride–Iodide Composite

Chan

Ong

Yen

et al. 2018

Helvetica Chimica Acta

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A new and concise protocol for selective reduction of N,N‐dimethylamides into aldehydes was established using sodium hydride (NaH) in the presence of sodium iodide (NaI) under mild reaction conditions. The present protocol with the NaH‐NaI composite allows for reduction of not only aromatic and heteroaromatic but also aliphatic N,N‐dimethylamides with wide substituent compatibility. Retention of α‐chirality in the reduction of α‐enantioriched amides was accomplished. Use of sodium deuteride (NaD) offers a new step‐economical alternative to prepare deuterated aldehydes with high deuterium incorporation rate. The NaH‐NaI composite exhibits unique chemoselectivity for reduction of N,N‐dimethylamides over ketones.

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Section: Introductionmentioning

confidence: 99%

Reduction of N,N‐Dimethylcarboxamides to Aldehydes by Sodium Hydride–Iodide Composite

Chan

Ong

Yen

et al. 2018

Helvetica Chimica Acta

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“…The process lies in the condensation of a protected a-aminoaldehyde (the Fmoc-leucinal) 4 [21] with the Nterminus of the growing peptide 5 to form an imine 6, which is subsequently reduced to amine 7 [22]. The N-amino link j[CO-N(NH 2 )] has been introduced as a dipeptide building-block, which was previously synthesized in liquid phase (Scheme 2).…”

Section: Chemistrymentioning

confidence: 99%

“…Fmoc-leucinal 4 was synthesized according to the procedure described by Douat et al [21]. The ''Weinreb morpholine amide'' was prepared, purified (see characterization below) and reduced by LiAlH 4 to produce 4, which is used without further purification.…”

Section: Fmoc-leu-h (4)mentioning

confidence: 99%

Development of pseudopeptides and peptidomimetics as eukaryote proteasome inhibitors

Basse

Felten

Papapostolou

et al. 2009

Comptes Rendus. Chimie

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“…Morpholinyl amides are as useful as Weinreb amides. [150][151][152] A variety of organometallic reagents, such as Grignard reagents, alkyllithiums, and metal hydrides, react with morpholinyl amide through a reaction mechanism similar to that of the Weinreb amide, affording the corresponding ketone or aldehyde in good yield. When a,b-unsaturated morpholinyl amide 87 was used as a substrate, in stark contrast to the Weinreb amide 85, 10 mol% of 85 afforded the corresponding a,b-epoxy morpholinyl amide 86 in quantitative yield and excellent enantiomeric excess (99% ee).…”

Section: Catalytic Asymmetric Epoxidation 3-1 Catalytic Asymmetric Ementioning

confidence: 99%

Enantioselective Total Syntheses of Several Bioactive Natural Products Based on the Development of Practical Asymmetric Catalysis

Ohshima

2004

CHEMICAL & PHARMACEUTICAL BULLETIN

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I present herewith enantioselective total syntheses of several bioactive natural products, such as (؊)-strychnine, (؉)-decursin, (؊)-cryptocaryolone diacetate, (؊)-fluoxetine, and aeruginosin 298-A, based on practical asymmetric catalyses (Michael reaction, epoxidation, and phase-transfer reaction) that I developed with coworkers in Prof. Shibasaki's group over the past 5 years. In the first part of this review, I discuss the great improvement of catalyst efficiency in an ALB-catalyzed asymmetric Michael reaction of malonate and application to the pre-manufacturing scale (greater than kilogram scale) and enantioselective total synthesis of (؊)-strychnine with the development of novel domino cyclization. To broaden the substrate generality of the Michael reaction, we developed a highly stable, storable, and reusable La-O-linked-BINOL complex. Further extension of the reaction using b b-keto ester as a Michael donor was achieved with the development of a La-NR-linked-BINOL complex, thereby improving indole alkaloid syntheses. In the second section, I discuss enantioselective total synthesis of (؉)-decursin using catalytic asymmetric epoxidation. To achieve the synthesis, we developed a new La-BINOL-Ph 3 As‫؍‬O (1 : 1 : 1) complex catalyst system, which has much higher reactivity and broader substrate generality than the previously developed catalyst systems. This allowed us to achieve catalytic asymmetric epoxidation of a a,b b-unsaturated carboxylic acid derivatives with high enantioselectivity and broad substrate generality for the first time by changing the lanthanide metal and reaction conditions. Among them, catalytic asymmetric epoxidation of a a,b b-unsaturated morpholinyl amides is quite useful in terms of synthetic utility of the corresponding a a,b b-epoxy morpholinyl amides. Highly catalyst-controlled enantio-or diastereoselective epoxidation of the a a,b b-unsaturated morpholinyl amides, coupled with diastereoselective reduction of b b-hydroxy ketones, enabled the synthesis of all possible stereoisomers of 1,3-polyol arrays with successful enantioselective total synthesis of several 1,3-polyol natural products, such as (؊)-cryptocaryolone diacetate. In addition, the development of a new regioselective epoxide-opening reaction of a a,b b-epoxy amides to the corresponding a a-and b b-hydroxy amides enhanced the usefulness of the present epoxidation and was applied to the enantioselective total synthesis of (؊)-fluoxetine. In the final section, I report the development of a new asymmetric two-center organocatalyst (TaDiAS) and its application to the enantioselective synthesis of aeruginosin 298-A and its analogues. Because of the remarkable structural diversity of TaDiAS, a practical asymmetric phase-transfer reaction with broad substrate generality was achieved. As a result, we succeeded in developing a highly versatile synthetic method for aeruginosin 298-A and its analogues. Inhibitory activity studies of the compounds against the serine protease trypsin provided preliminary information about their str...

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Synthesis of N-protected α-amino aldehydes from their morpholine amide derivatives

Cited by 70 publications

References 9 publications

Reduction of N,N‐Dimethylcarboxamides to Aldehydes by Sodium Hydride–Iodide Composite

Reduction of N,N‐Dimethylcarboxamides to Aldehydes by Sodium Hydride–Iodide Composite

Development of pseudopeptides and peptidomimetics as eukaryote proteasome inhibitors

Enantioselective Total Syntheses of Several Bioactive Natural Products Based on the Development of Practical Asymmetric Catalysis

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