Asymmetric synthesis of enantiopure isoxazolidinone monomers for the synthesis of β3-oligopeptides by chemoselective amide ligation

Juarez-Garcia, M. Elisa; Yu, Shouyun; Bode, Jeffrey W.

doi:10.1016/j.tet.2010.04.016

Cited by 29 publications

(15 citation statements)

References 44 publications

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“…[α] D 22 +40.10 (c 1.0, CHCl 3 ); 1 H-NMR (400 MHz, CDCl 3 ) δ 7.22–7.30 (m, 5H), 4.58–4.65 (m, 1H), 3.04 (dd, J = 8.5 Hz, 12 Hz, 1H), 2.74–2.85 (m, 2H), 2.57 (dd, J = 4.7 Hz, 16 Hz, 1H), 1.27 (s, 9H). Spectroscopic data are in agreement with reference [ 22 ]. 92% ee; Chiral HPLC condition: SHIMADZU Essentia LC-16 HPLC, Chiralcel AD-H column (250 × 4.6 mm, i.d.)…”

Section: Methodssupporting

confidence: 90%

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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Section: Methodssupporting

confidence: 90%

Practical Asymmetric Synthesis of Sitagliptin Phosphate Monohydrate

Gao

et al. 2018

Molecules

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“…[14] The ring-opening sequenceo ft he sterically hindered 6a was achieved in the presence of BnNH 2 in refluxing tert-butanol allowingt he construction of the corresponding b 2,2 -aminoa mide product 12 in 87 % isolated yield. Given the powerful KAHA chemicall igation, developed by the group of Bode between hydroxylamine pendants of b-aminoa cids and ketoacids, [23] this type of product 12 might be useful in b-peptide synthesis.…”

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confidence: 99%

Enantioselective Phase‐Transfer Catalyzed α‐Sulfanylation of Isoxazolidin‐5‐ones: An Entry to β^2,2‐Amino Acid Derivatives

Cadart

Berthonneau

Levacher

et al. 2016

Chemistry A European J

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An unprecedented enantioselective α-functionalization of C4-substituted N-alkoxycarbonyl isoxazolidin-5-ones, readily available platforms from Meldrum's acid derivatives, by N-sulfanylphthalimide (PhthSR) electrophiles was achieved upon an efficient phase-transfer catalytic approach, mediated by a commercial N-spiro quaternary ammonium catalyst. Two catalytic activities of the in situ formed R N Phth species were highlighted, the phtalimidate being involved in the anion metathesis event and likely as a Brønsted base. This sequence offers a straightforward access to α,α-disubstituted isoxazolidinones, which turned out to be useful precursors of α-sulfanyl-β -amino acid derivatives.

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“…We have recently reported synthetic approaches to enantiopure, unnatural  3 -amino acids and  3 -N-hydroxyaminoacids suitable for the proposed studies (Scheme 1). 10 First, we have developed a practical and scalable approach to enantiopure  3 -amino acids that is particularly well suited for the synthesis of unnatural derivatives where the corresponding enantiopure -amino acid is not available.…”

Section: Figure 1 Primary Structure Of Surfactin and The Two Aza-dermentioning

confidence: 99%

Synthesis of Aza-Surfactin and 3-Epi-Aza-Surfactin

Bode¹,

Huang²,

Juarez-Garcia³

et al. 2012

HETEROCYCLES

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Two synthetic approaches to aza-surfactins are reported. In the first, our recently developed synthesis of unnatural  3-amino acids was used to prepare the requisite monomer, which was used in solid phase peptide synthesis, and followed by macrolactamization of a partially protected precursor. In the second, the corresponding  3-N-hydroxyaminoacid was used to prepare a fully unprotected cyclization precursor that was closed to give 3-epi-aza-surfactin by the first example of cyclization by the -ketoacid-hydroxylamine amide formation. Dedicated to Professor Albert Padwa on the occasion of his 75 th birthday INTRODUCTION Surfactin, the principle member of the lipopeptides, is a powerful antibiotic with a unique mechanism. 1 This growing class of natural products is produced by the genus Bacillus and has found application not only as antibiotics but also as antivirals, fibrin clot inhibitors, and other biological applications. 2 Their mode of action is thought to be membrane permeabilization by a detergent-like disruption of the lipid bilayer along with complexation and transport of ions through the membrane. The precise mechanism, however, remains unknown and several competing theories have been proposed. 3 Several different surfactin structures are known but they all share a common architecture: seven α-amino acids joined as a depsipeptide by macrolactonization with a β-hydroxy fatty acid. Structural studies with NMR techniques reveal a characteristic saddle-horse shape. 4 The long alkyl hydrocarbon chains and their cyclic cores endow these peptides with an amphipathic nature, which allow them to penetrate the membrane and disturb the target cells. Surfactin has attracted considerable attention for their potential medical applications. Improvements to the bioactivity, particularly to reduced toxicity, may be gained by modification of their cyclic peptide core. To date surfactin has been produced almost exclusively by

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Asymmetric synthesis of enantiopure isoxazolidinone monomers for the synthesis of β3-oligopeptides by chemoselective amide ligation

Abstract: The design and general synthesis of enantiopure isoxazolidinone monomers as precursors for the preparation of enantiopure N-terminal hydroxylamine-β 3 -oligopeptides, which may be used as reaction partners with α-ketoacids in the decarboxylative amide ligation reaction, is described.

Cited by 29 publications

References 44 publications

Practical Asymmetric Synthesis of Sitagliptin Phosphate Monohydrate

Practical Asymmetric Synthesis of Sitagliptin Phosphate Monohydrate

Enantioselective Phase‐Transfer Catalyzed α‐Sulfanylation of Isoxazolidin‐5‐ones: An Entry to β^2,2‐Amino Acid Derivatives

Synthesis of Aza-Surfactin and 3-Epi-Aza-Surfactin

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Asymmetric synthesis of enantiopure isoxazolidinone monomers for the synthesis of β3-oligopeptides by chemoselective amide ligation

Abstract: The design and general synthesis of enantiopure isoxazolidinone monomers as precursors for the preparation of enantiopure N-terminal hydroxylamine-β 3 -oligopeptides, which may be used as reaction partners with α-ketoacids in the decarboxylative amide ligation reaction, is described.

Cited by 29 publications

References 44 publications

Practical Asymmetric Synthesis of Sitagliptin Phosphate Monohydrate

Practical Asymmetric Synthesis of Sitagliptin Phosphate Monohydrate

Enantioselective Phase‐Transfer Catalyzed α‐Sulfanylation of Isoxazolidin‐5‐ones: An Entry to β2,2‐Amino Acid Derivatives

Synthesis of Aza-Surfactin and 3-Epi-Aza-Surfactin

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Enantioselective Phase‐Transfer Catalyzed α‐Sulfanylation of Isoxazolidin‐5‐ones: An Entry to β^2,2‐Amino Acid Derivatives