Synthesis of Oxazinanones: Intramolecular Cyclization of Amino Acid-Derived Diazoketones via Silica-Supported HClO4 Catalysis

Gallo, Rafael D. C.; Campovilla, Orlando C.; Ahmad, Anees; Burtoloso, Antonio C. B.

doi:10.3389/fchem.2019.00062

Cited by 6 publications

(3 citation statements)

References 39 publications

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“…1 H NMR (400 MHz, chloroform-d): δ 5.38 (s, 1H), 5.30 (d, J = 9.4 Hz, 1H), 3.94 (d, J = 9.4 Hz, 1H), 1.44 (s, 9H), 1.01 (s, 9H). 13 (16); 96 (20); 70 (23); 59 (10); 57 (75); 56 (24); 55 (12); 44 (11); 43 (10); 41 (57); 39 (22) (S)-tert-Butyl (4-Diazo-3-oxo-1-phenylbutan-2-yl)carbamate (2d). Yellow crystalline powder, yield = 85% (184 g).…”

Section: Synthesis Of Bromoketonesmentioning

confidence: 99%

“…int. ): 313 (1); 211 (4); 210 (4); 209 (5); 208 (4); 194 (5); 192 (5); 186 (3); 168 (3); 166 (9); 164 (4); 151 (3); 150 (4); 149 (2); 148 (4); 130 (38); 123 (14); 121 (11); 116 (11); 98 (33); 95 (16); 93 (19); 86 (18); 70 (12); 59 (38); 57 (90); 56 (63); 55 (53); 53 (10); 51 (14); 50 (18); 44 (43); 43 (18); 42 (32); 41 (98); 39 (100); 38 (18) (22); 130 (5); 123 (8); 100 (13); 88 (17); 70 (14); 69 (10); 59 (32); 58 (20); 57 (100); 56 (16) tert-Butyl (3-Bromo-2-oxopropyl)(methyl)carbamate (3g), Orange Oil. Yield = 89% (181 g).…”

Section: Synthesis Of Bromoketonesunclassified

“…Therefore, these reagents could be considered as part of a chiral pool. , Recently, several preparative methods for synthesizing MedChem-relevant compounds based on AADDK reagents have been developed . In particular, preparations of chiral β-amino acids, azetidin-3-ones, , lactams, , oxazinones, dihydropyridones, N -protected α-aminoglyoxals, and hetarylaminomethyl derivatives are worth mentioning (Figure A). Despite the existing alternative approaches to the preparation of AADDKs that emerged in the literature, ,, interaction of activated derivatives of N -protected amino acids with diazomethane still remains the most efficient method .…”

Section: Introductionmentioning

confidence: 99%

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Practical Synthetic Method for Amino Acid-Derived Diazoketones Shelf-Stable Reagents for Organic Synthesis

Pendiukh,

Yakovleva,

Stadniy

et al. 2023

Org. Process Res. Dev.

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A novel approach for safe generation of diazomethane-contained organic solution was proposed using a serial flow reactor. The productivity of diazomethane generation reached 0.45 mol/h. Several chiral diazoketones have been prepared in quantities up to 150 g through the reaction of diazomethane with mixed anhydrides, generated in situ by the treatment of Bocprotected α-amino acids with ethyl chloroformate. The synthesized diazoketones are crystalline substances stable up to 110−142 °C and can easily be purified on silica gel and stored for a long term. The overall stability and availability on a large scale allow considering such diazoketones as promising bench-stable reagents for a broad scope of applications. The quantum chemical studies show that the stability of diazoketones is connected with conjugation of the carbonyl group with the diazo moiety. As an example of applicability, the reaction of diazoketones with concentrated HBr gives the corresponding pure chiral α-bromoketones without additional purification.

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Section: Synthesis Of Bromoketonesmentioning

confidence: 99%

Section: Synthesis Of Bromoketonesunclassified

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Practical Synthetic Method for Amino Acid-Derived Diazoketones Shelf-Stable Reagents for Organic Synthesis

Pendiukh,

Yakovleva,

Stadniy

et al. 2023

Org. Process Res. Dev.

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Chemoenzymatic Synthesis of O‐Containing Heterocycles from α‐Diazo Esters

Mittmann

Peschke

et al. 2019

ChemCatChem

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The synergy of biocatalysis and transition metal catalysis is rapidly moving forward, providing increasingly effective workflows in chemical synthesis. Here we present a facile way to prepare synthetically challenging O‐containing heterocycles bearing disubstituted stereogenic centers via catalytic chemoenzymatic transformation of α‐diazo carbonyl compounds. We demonstrate that keto‐α‐diazoesters can be enzymatically reduced to the corresponding alcohols with exquisite enantioselectivity and under retention of the diazo group using the ketoreductases LbADH and Gre2p. To further functionalize the resulting enantiopure (R)‐ and (S)‐hydroxyl α‐diazo esters, a variety of Cu and Rh catalysts were screened for intramolecular ring closure. Six‐ and seven‐membered rings with both, aliphatic and ester substituents, were obtained with up to 93 : 7 diastereomeric ratio and 81 % yield. Up to 98 % enantiomeric excess was obtained for both diastereomers, yielding the thermodynamically less favored α,ω‐trans‐oxepanes as the main products.

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Reaction Pathways in Carbonates and Esters

Tundo,

Aricò

2023

ChemSusChem

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This review reports on the competition/collaboration among intertwined base‐catalyzed acyl cleavage bimolecular mechanism (BAc2)/base‐catalyzed alkyl cleavage bimolecular mechanism (BAl2) or the related acid catalyzed mechanisms AAc2/AAl2 and AAl1 concerning Carbonates chemistry also in comparison with Esters reactivity. A consistent analysis of the experimental data so far available in the literature led to proposing a Model outlining the differences in energy profiles among the above‐mentioned reaction mechanisms. The reactions involving Carbonates are so tightly interconnected that the formation of the final product is driven by a precise not interfering sequence of BAc2‐BAl2 (or AAl2‐AAc2) mechanisms. When entropic effect (in cyclizations) or an anchimneric effect (mustard carbonates, isosorbide methylation) are involved, the difference in Gibbs activation energy is reduced allowing chemical transformations that would normally require higher temperatures. In these cases (intramolecular alkylation, cyclisation reaction, and alkylation by mustard carbonates) only a catalytic amount of base is required as the leaving group CH3OCOO‐ decomposes restoring the base. As Green Chemistry is concerned, syntheses with much lower environmental impact are achieved with Carbonates when compared with the corresponding ones involving Chlorine chemistry.

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Synthesis of Oxazinanones: Intramolecular Cyclization of Amino Acid-Derived Diazoketones via Silica-Supported HClO4 Catalysis

Cited by 6 publications

References 39 publications

Practical Synthetic Method for Amino Acid-Derived Diazoketones Shelf-Stable Reagents for Organic Synthesis

Practical Synthetic Method for Amino Acid-Derived Diazoketones Shelf-Stable Reagents for Organic Synthesis

Chemoenzymatic Synthesis of O‐Containing Heterocycles from α‐Diazo Esters

Reaction Pathways in Carbonates and Esters

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