An unexpected Mitsunobu reaction. A direct route to the 2,5-diazabicyclo[2.2.1]heptan-3-one skeleton as a γ-lactam mimic of β-lactam antibiotics

Hadfield, Peter S.; Galt, R. H. B.; Sawyer, Yvonne; Layland, Nicola J.; Page, Michael I.

doi:10.1039/a604564b

Cited by 11 publications

(6 citation statements)

References 10 publications

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“…Bicyclic γ-lactams 356 , competitive inhibitors of β-lactamases, were efficiently synthesized using intramolecular coupling reactions of amide functionalities 355 with alcohols in the solid phase (Scheme a) . An earlier study by Page and co-workers involved a similar lactam formation in solution phase . Such annulations leading to five-membered rings are generally straightforward, and a solid phase synthesis of imidazolones 357 has been reported recently (Scheme b) .…”

Section: Amines Amides (Including Nucleobases) or Azides As Nucleophilesmentioning

confidence: 99%

Mitsunobu and Related Reactions: Advances and Applications

et al. 2009

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His research interests include Organophosphorus Chemistry and Main Group Chemistry. He has over 115 publications so far and is a fellow of the Indian Academy of Sciences, Bangalore. N. N. Bhuvan Kumar was born in Cherukupalli, Guntur, India. After completing his B.Sc. from Nagarjuna University, he joined the School of Chemistry, University of Hyderabad, as a postgraduate student in the year 2000 and obtained his Master's degree in Chemistry. Currently, he is pursuing a Ph.D. on Organophosphonates under the supervision of Prof. K. C. Kumara Swamy. E. Balaraman was born in Kancheepuram, Chennai, India, in 1980. He received his M.Sc. in Chemistry from Vivekananda College [Madras University (2002)] and his Ph.D. degree in the areas of organophosphonates and modified BINOLs under the guidance of Prof. K. C. Kumara Swamy. Presently he is a postdoctoral fellow with Professors David Milstein and Ronny Neumann at the Weizmann Institute of Science, Israel. K. V. P. Pavan Kumar was born in Hyderabad (Andhra Pradesh), India, in 1979. He obtained his B.Sc. (Chemistry Honors) and M.Sc. (Chemistry) degrees from Sri Sathya Sai Institute of Higher Learning, Puttaparthi, A.P., India. He obtained his Ph.D. degree under the guidance of Prof. K. C. Kumara Swamy in October 2006. Presently he is working as a postdoctoral fellow in the area of hydroamination reactions using new titanium catalysts with Prof. Pierre Le Gendre at the Universite ´de Bourgogne, France.

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Section: Amines Amides (Including Nucleobases) or Azides As Nucleophilesmentioning

confidence: 99%

Mitsunobu and Related Reactions: Advances and Applications

et al. 2009

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“…This first-generation process was a modification of our previously reported procedure, which we described as a medicinal chemical process for the synthesis of another N -BOC-protected aminomethylpyrrolidine derivatives. The hydroxyproline 4 was treated with 4-nitrobenzyl chloroformate (PNZ-Cl) in toluene−water to give N -protected 4-hydroxyproline 5 in 88% yield. The hydroxyproline 5 was converted into hydroxymethylpyrrolidine 8 in a one-pot procedure in 93% overall yield by a sequence of three reactions at −45 °C, namely the formation of mixed anhydride 6 from hydroxyproline 5 with ethyl chloroformate and triethylamine (Et 3 N), the O -mesylation of mixed anhydride 6 with methanesulfonyl chloride (MsCl) and Et 3 N, and the reduction of the mixed anhydride 7 with sodium borohydride (NaBH 4 ).…”

Section: Resultsmentioning

confidence: 99%

Practical Large-Scale Synthesis of the 2-Aminomethylpyrrolidin-4-ylthio-Containing Side Chain of the Novel Carbapenem Antibiotic Doripenem

Nishino

Komurasaki

Yuasa

et al. 2003

Org. Process Res. Dev.

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The first synthesis using an original procedure and a practical large-scale process using an improved procedure for the synthesis of the N-PNZ-protected 2-aminomethylpyrrolidin-4-ylthio-containing side chain of doripenem hydrate (S-4661), a novel parenteral 1 -methylcarbapenem antibiotic, are described. trans-4-Hydroxy-L-proline (4) was converted in an efficient process to (2S,4S)-4-acetylthio-2-(N-sulfamoyl-tertbutoxycarbonylaminomethyl)-1-(4-nitrobenzyloxycarbonyl)pyrrolidine (3) in 55-56% overall yield via a six-step sequence, which includes the two alternative routes to intermediate 13. This process requires no chromatographic purifications, no cryogenic temperatures, no haloalkane solvents, and short operating times and is amenable to a multikilogram-scale preparation. Several kilograms of the side chain 3 were successfully prepared by this process.

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“…As in the case of β-lactams, a γ-lactam ring is also readily formed under the conditions of the Mitsunobu reaction [42][43][44]. Thus, a series of enantiomerically pure 3-aminopyrrolidinones 35 was obtained from (S)-homoserine lactone 36 [42].…”

Section: The Production Of Five-membered Ringsmentioning

confidence: 96%

“…In the case of R = Bn a diastereomer of 39 was also isolated from the reaction mixture with a yield of 10%. The bicyclic compounds 40 containing a γ-lactam fragment were obtained from the anilides of N-protected (2S,4R)-3-hydroxyproline 41 [44]. Cyclization did not occur if the benzylamide (41, R 1 = Bn, R 2 = 4-O 2 NC 6 H 4 CH 2 ) was used instead of the anilides, and the monocyclic derivative, formed as a result of S N 2 substitution with the participation of the anion of diethyl hydrazinedicarboxylate, was isolated.…”

Section: The Production Of Five-membered Ringsmentioning

confidence: 99%

The Mitsunobu reaction in the chemistry of nitrogen-containing heterocyclic compounds. The formation of heterocyclic systems (review)

Голанцов

Карчава

Yurovskaya

2008

Chem Heterocycl Comp

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Methods for the design of nitrogen-containing heterocyclic systems involving the formation of C-N bonds under the conditions of the Mitsunobu reaction are discussed.The Mitsunobu reaction [1][2][3][4] is the reaction of compounds containing a mobile hydrogen atom HX with alcohols in the presence of a reagent system consisting of an azodicarboxylic ester and a phosphine PR 1 3 . This reaction results in the formation of an alkylation product RX accompanied by oxidation of the phosphine PR 1 3 to phosphine oxide R 1 3 P=O and reduction of the azodicarboxylic ester to the corresponding hydrazine.The reaction takes place under very mild conditions and usually at room temperature. If a chiral secondary alcohol ROH is used, the reaction is usually stereospecific and is accompanied by inversion of the configuration at the asymmetric carbon atom of the alcohol [1-3].From the moment of the first report [5] the Mitsunobu reaction became a powerful tool in synthetic organic chemistry and found widespread use in the synthesis of various heterocyclic compounds, optically active substances, steroids, alkaloids, carbohydrates, and nucleosides [1][2][3][4]6]. In particular, in a number of cases the Mitsunobu reaction has made it possible to synthesize new physiologically active compounds or to put forward new highly effective approaches to synthesis. Several reviews have been devoted to the Mitsunobu reaction [1-4, 6, 7]. Data on the use of the Mitsunobu reaction in the synthesis of alkaloids were reviewed in [6]. Various experimental techniques that make it possible to simplify the isolation of the products of the Mitsunobu reaction RX from the reaction mixture, including the use of reagents attached to a polymer support, were discussed in [7]. _______ * Dedicated to Afanasi Andreevich Akhrem on his 95th birthday. _________________________________________________________________________________________

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An unexpected Mitsunobu reaction. A direct route to the 2,5-diazabicyclo[2.2.1]heptan-3-one skeleton as a γ-lactam mimic of β-lactam antibiotics

Cited by 11 publications

References 10 publications

Mitsunobu and Related Reactions: Advances and Applications

Mitsunobu and Related Reactions: Advances and Applications

Practical Large-Scale Synthesis of the 2-Aminomethylpyrrolidin-4-ylthio-Containing Side Chain of the Novel Carbapenem Antibiotic Doripenem

The Mitsunobu reaction in the chemistry of nitrogen-containing heterocyclic compounds. The formation of heterocyclic systems (review)

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