Asymmetric Synthesis of Maraviroc (UK‐427,857)

Zhao, Gui‐Ling; Lin, Shuangzheng; Korotvička, Aleš; Deiana, Luca; Kullberg, Martin; Córdova, Armando

doi:10.1002/adsc.201000287

Cited by 48 publications

(21 citation statements)

References 39 publications

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“…[22] In contrast, employing an N-aryl-or N-alkyl-substituted hydroxylamine as the substrate leads to enantioselective intra-or intermolecular 1,3-dipolar cycloadditions [Eqs. (2)(3)].…”

Section: Introductionmentioning

confidence: 99%

“…[18] Based on our research interest in asymmetric catalysis and green chemistry, [19] we have explored aminocatalytic one-pot asymmetric tandem and multicomponent transformations [20][21] between hydroxylamines and a,b-unsaturated aldehydes. [22][23][24] We found that the transformations exhibit completely different chemoselectivity depending on the substituent at the N atom of the hydroxyl amine derivative, which affects its pK a [Eqs.…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Asymmetric Aziridination of α,β‐Unsaturated Aldehydes

Deiana

Dziedzic

Zhao

et al. 2011

Chemistry A European J

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The development, scope, and application of the highly enantioselective organocatalytic aziridination of α,β-unsaturated aldehydes is presented. The aminocatalytic azirdination of α,β-unsaturated aldehydes enables the asymmetric formation of β-formyl aziridines with up to >19:1 d.r. and 99% ee. The aminocatalytic aziridination of α-monosubstituted enals gives access to terminal α-substituted-α-formyl aziridines in high yields and up to 99% ee. In the case of the organocatalytic aziridination of disubstituted α,β-unsaturated aldehydes, the transformations were highly diastereo- and enantioselective and give nearly enantiomerically pure β-formyl-functionalized aziridine products (99% ee). A highly enantioselective one-pot cascade sequence based on the combination of asymmetric amine and N-heterocyclic carbene catalysis (AHCC) is also disclosed. This one-pot three-component co-catalytic transformation between α,β-unsaturated aldehydes, hydroxylamine derivatives, and alcohols gives the corresponding N-tert-butoxycarbonyl and N-carbobenzyloxy-protected β-amino acid esters with ee values ranging from 92-99%. The mechanisms and stereochemistry of all these catalytic transformations are also discussed.

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“…[22] In contrast, employing an N-aryl-or N-alkyl-substituted hydroxylamine as the substrate leads to enantioselective intra-or intermolecular 1,3-dipolar cycloadditions [Eqs. (2)(3)].…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Catalytic Asymmetric Aziridination of α,β‐Unsaturated Aldehydes

Deiana

Dziedzic

Zhao

et al. 2011

Chemistry A European J

Self Cite

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“…Previous studies from our group [26] and those of Córdova [27,28] and Vicario [20] had shown that the use of chiral diarylprolinol-silyl ethers as catalysts led to high enantioselectivities in the aza-Michael/cyclization reactions of β-substituted [20,27,28] and of α,β-disubstituted [26] enals with hydroxylamines or hydrazines. However, α-branched vinyl carbonyls remain a very challenging substrate for this type of reaction and only one successful example of aminocatalytic asymmetric aza-Michael addition to α-substituted vinyl ketones has been reported so far [29,30].…”

Section: Resultsmentioning

confidence: 99%

Expedient Organocatalytic Syntheses of 4-Substituted Pyrazolidines and Isoxazolidines

et al. 2016

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Abstract:The efficient organocatalytic synthesis of heterocyclic systems of biological relevance is a subject of growing interest. We have found that the pyrrolidine/benzoic acid-catalyzed reaction of α-substituted propenals such as methacrolein, 2-benzylpropenal and 2-(n-hexyl)propenal with activated hydrazines takes place in very good yields (83%-99.6%) under very mild conditions to afford 4-substituted pyrazolidin-3-ols (as diastereomer mixtures); subsequent oxidation with PCC affords the corresponding-4-substituted-3-pyrazolidinones in essentially quantitative yields. In a similar way, 4-substituted isoxazolidinones are obtained with N-Cbz-hydroxylamine as a reagent. The use of chiral diarylprolinol trimethylsilyl ethers as catalysts allows the synthesis of several of these compounds in optically active form, in some cases with excellent enantioselectivity (up to 96:4 er). A preliminary evaluation of the biological activity shows that some of these compounds exhibit interesting antibacterial and antifungal activities.

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“…In the last decades, a variety of chiral amino acids can be made from hemiacetals through catalytic tandem aza-Michael/hemiacetal reaction, using organocatalyst in high yield and enantioselectivity [ 15 , 16 , 17 , 18 , 19 ]. As part of our efforts to develop efficient and practical access to stigliptin phosphate monohydrate, we herein report an efficient synthetic route to make sitagliptin phosphate monohydrate by means of chiral hemiacetal as the key intermediate.…”

Section: Introductionmentioning

confidence: 99%

Practical Asymmetric Synthesis of Sitagliptin Phosphate Monohydrate

Gao

et al. 2018

Molecules

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Optically pure sitagliptin phosphate monohydrate is efficiently and practically synthesized through a chiral hemiacetal as the key intermediate in 54% overall yield starting from (E)-4-(2,4,5-trifluorophenyl)but-2-enal and N-boc-protected hydroxylamine. The chiral hemiacetal fragment is constructed by a tandem aza-Michael/hemiacetal reaction catalyzed by an organocatalyst and the influence of acidity of Brønsted acid on tandem aza-Michael/hemiacetal reaction is researched in detail.

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Asymmetric Synthesis of Maraviroc (UK‐427,857)

Cited by 48 publications

References 39 publications

Catalytic Asymmetric Aziridination of α,β‐Unsaturated Aldehydes

Catalytic Asymmetric Aziridination of α,β‐Unsaturated Aldehydes

Expedient Organocatalytic Syntheses of 4-Substituted Pyrazolidines and Isoxazolidines

Practical Asymmetric Synthesis of Sitagliptin Phosphate Monohydrate

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