Stereoselective reduction and reductive dephosphonylation of β-iminophosphonates

Amedjkouh, Mohamed; Grimaldi, J.

doi:10.1016/s0040-4039(02)00521-x

Cited by 11 publications

(4 citation statements)

References 24 publications

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“…In this context, Oh and coworkers 16 have reported a method for C-P bond cleavage in b-oxo phosphonates by dephosphonylation of their lithium enolates with lithium aluminum hydride. Additionally, Amedjkouh and Grimaldi 17 have reported the dephosphonylation of 5-phosphonylpyrrolidines using the same reducing agent. According to these methods, we carried out the reaction of the 3-oxoisoindolin-1-ylphosphonates 7a-h with lithium aluminum hydride in anhydrous tetrahydrofuran at 0 to 25°C, whereupon the desired isoindolin-1-ones 1-3 were obtained in moderate to good yield (Scheme 1).…”

Section: Figurementioning

confidence: 98%

An Easy Approach for the Synthesis of N-Substituted Isoindolin-1-ones

Ordóñez¹,

Tibhe²,

Zamudio‐Medina³

et al. 2012

Synthesis

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A practical and efficient two-step synthesis of N-substituted isoindolin-1-ones was developed. The one-pot reaction of 2-formylbenzoic acid with amines and dimethyl phosphite proceeds in short time either with conventional heating or microwave irradiation under catalyst-free conditions to afford the corresponding Nsubstituted dimethyl 3-oxoisoindolin-1-ylphosphonates in good yield which, by means of a dephosphonylation reaction with lithium aluminum hydride, give the target N-substituted isoindolin-1-ones in moderate to good yield.Isoindolin-1-ones (2,3-dihydro-1H-isoindol-1-ones) have gained considerable attention recently due to their fascinating properties and potential applications in many fields, especially in biology and medicinal science. 1 The interest in these heterocyclic compounds stems mainly from their diverse biological activities. For example, isoindolin-1-ones 1-3 ( Figure 1) have been tested as antimicrobial agents, 2 while indoprofen (4) has been shown to have anti-inflammatory activity 3,4 and deoxythalidomide (5) is an inhibitor of tumor necrosis factor production. 5 Additionally, the isoindolin-1-one skeleton is a key intermediate for the synthesis of many naturally occurring bioactive compounds. 6 Figure 1Consequently, the chemistry of isoindolinones has attracted much attention, and a number of synthetic strategies have been developed over the past few years including the reduction of phthalimides, 7 the condensation of anilines with o-phthalaldehydes, 8 amination and lactamization of 2-carbomethoxybenzaldehyde, 6h,9 palladium(0)-catalyzed carbonylation-amination, 10 synthesis from isocyanates 11 and base-induced aryne-mediated cyclization of o-halo-N-(phosphinylmethyl)benzamide derivatives; 12,13 however, despite their potential utility, these procedures typically suffer from one or more disadvantages, such as the use of harsh conditions or tedious multisteps which are necessary for these syntheses. Thus, there is still a need to develop versatile and flexible methods for the synthesis of isoindolin-1-ones. In this context, herein we describe an efficient method for the synthesis of N-substituted isoindolin-1-ones. Our synthetic strategy is based upon a onepot reaction of 2-formylbenzoic acid with alkyl-or arylamines and dimethyl phosphite using conventional heating or microwave irradiation under catalyst-free conditions, 14 followed by a dephosphonylation reaction.We have recently developed 15 an efficient and highly diastereoselective method for the synthesis of 3-oxoisoindolin-1-ylphosphonate 7a by a three-component, one-pot reaction of 2-formylbenzoic acid (6), (S)-a-methylbenzylamine and dimethyl phosphite under catalyst-and solvent-free conditions (Table 1, entry 1). To establish the generality of this three-component, one-pot process we carried out the reaction of 2-formylbenzoic acid (6) with either alkyl-or arylamines and dimethyl phosphite. Thus, the reaction of 2-formylbenzoic acid (6) with tert-butylamine or benzhydrylamine and dimethyl phosphite at 80°C under catalyst-and sol...

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Section: Figurementioning

confidence: 98%

An Easy Approach for the Synthesis of N-Substituted Isoindolin-1-ones

Ordóñez¹,

Tibhe²,

Zamudio‐Medina³

et al. 2012

Synthesis

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“…1-Pyrroline 326d − f can also be reduced using NaBH 4 in ethanol at −20 °C. Under these conditions, no dephosphorylation occurs and only the cis -pyrrolidine is formed …”

Section: 511 Addition To An Allenic Moietymentioning

confidence: 99%

Synthetic Methods for Azaheterocyclic Phosphonates and Their Biological Activity

2004

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“…Subsequently, a single stereoisomer of 3r was treated with 1 n hydrochloric acid, and the desired cyclization product 6 was obtained in 95 % isolated yield without any erosion of its enantiopurity. Further reduction of (dihydropyrrolyl)phosphonate 6 with NaBH 4 in ethanol delivered the cyclic α‐aminophosphonic acid derivative 7 in 50 % yield with high diastereoselectivity (93:7 dr ) . 1 H‐ 1 H NOESY‐1D and NOESY‐2D analyses showed a trans relationship between the 3‐ and 5‐aryl groups of the major stereoisomer 7 (see Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

“…Further reduction of (dihydropyrrolyl)phosphonate 6 with NaBH 4 in ethanol delivered the cyclic α-aminophosphonic acid derivative 7 in 50 % yield with high diastereoselectivity (93:7 dr). [10] 1 H-1 H NOESY-1D and NOESY-2D analyses showed a trans relationship between the 3-and 5-aryl groups of the major stereoisomer 7 (see Supporting Information). Scheme 3.…”

Section: Introductionmentioning

confidence: 99%

Phase‐Transfer‐Catalyzed Asymmetric Michael Addition of (Iminomethyl)phosphonates to α,β‐Unsaturated Ketones: Access to α‐Aminophosphonic Acid Derivatives

Cui

Zhang

et al. 2017

Eur J Org Chem

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A phase‐transfer‐catalyzed asymmetric Michael addition of (iminomethyl)phosphonates to α,β‐unsaturated ketones is described. In the presence of 1 mol‐% of a chiral dinuclear N‐spiro ammonium salt, the addition reaction proceeded smoothly to afford the adducts in up to 97 % yield with up to 99:1 dr and 78 % ee. One of the products was readily converted into a cyclic α‐aminophosphonic acid derivative without any erosion of the enantiopurity.

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Stereoselective reduction and reductive dephosphonylation of β-iminophosphonates

Cited by 11 publications

References 24 publications

An Easy Approach for the Synthesis of N-Substituted Isoindolin-1-ones

An Easy Approach for the Synthesis of N-Substituted Isoindolin-1-ones

Synthetic Methods for Azaheterocyclic Phosphonates and Their Biological Activity

Phase‐Transfer‐Catalyzed Asymmetric Michael Addition of (Iminomethyl)phosphonates to α,β‐Unsaturated Ketones: Access to α‐Aminophosphonic Acid Derivatives

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