Stereoselective Amine Addition to Six‐Membered Cyclic Nitronates Promoted by Silyl Triflate

Mikhaylov, Andrey А.; Dilman, Alexander D.; Khomutova, Yulia A.; Arkhipov, Dmitry E.; Korlyukov, Alexander A.; Ioffe, Sema L.

doi:10.1002/ejoc.201300511

Cited by 17 publications

(9 citation statements)

References 21 publications

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“…Recently, in the study of C,N-coupling of sixmembered cyclic nitronates 1 with trialkylsilylamines [16], the reversibility of this important reaction was shown. Of course, now this factor has to be taken into account both in the analysis of coupling of (B') + cations with potential nucleophiles, and in the design of any new strategies related to iminium ((B') + cations.…”

Section: Analysis Of Kinetic Datamentioning

confidence: 99%

A New Algorithm for the Reactivity Umpolung of Aliphatic Nitro Compounds

et al. 2018

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A new four-stage algorithm for the reactivity umpolung of aliphatic nitro compounds has been proposed and experimentally confirmed. Bis(trialkylsilyloxy)iminium cations, which are key intermediates in the new scheme, have been qualitatively and quantitatively determined by the method of double nuclear magnetic resonance. Their thermodynamic parameters have been determined. The kinetics of coupling of these cations with π-nucleophiles has been measured experimentally, and the stereodynamics of the interaction of these cations has been discussed using a general model involving anomeric assistance. The utility and novelty of the proposed approach for the development of modern methodology of organic synthesis using available aliphatic nitro compounds as initial reagents have been demonstarted.

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Section: Analysis Of Kinetic Datamentioning

confidence: 99%

A New Algorithm for the Reactivity Umpolung of Aliphatic Nitro Compounds

et al. 2018

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“…19 rac-6,6-Dimethyl-4-phenethyl-5,6-dihydro-4H-1,2-oxazine 2-Oxide (2f). 21 Prepared from (E)-(4-nitrobut-3-en-1-yl)benzene 1c 22 (482 mg, 2.72 mmol) and 2-methylpropene (760 mg, 13.6 mmol taken as 5 M solution in CH 2 Cl 2 ) with SnCl 4 (0.38 mL, 3.26 mmol) in 12 mL of CH 2 Cl 2 . Reaction was conducted at −78 °C for 1.5 h, followed by an aqueous workup.…”

Section: ■ Conclusionmentioning

confidence: 99%

“…NMR spectra are in agreement with published data. 21 rac-3,6,6-Trimethyl-4-phenyl-5,6-dihydro-4H-1,2-oxazine 2-Oxide (2g). 23 Prepared from (E)-(2-nitroprop-1-en-1-yl)benzene 1d 24 (5.0 g, 30.7 mmol) and 2-methylpropene (3.4 g, 60.7 mmol) with SnCl 4 (3.5 mL, 30.0 mmol) in 110 mL of CH 2 Cl 2 .…”

Section: ■ Conclusionmentioning

confidence: 99%

Construction of Saturated Oxazolo[3,2-b][1,2]oxazines via Tandem [3+2]-Cycloaddition/[1,3]-Rearrangement of Cyclic Nitronates and Ketenes

et al. 2021

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Reaction of six-membered cyclic nitronates with disubstituted ketenes affords hitherto unknown saturated oxazolo[3,2-b][1,2]oxazines possessing up to four contiguous stereogenic centers. The process involves a tandem of [3+2]-cycloaddition across the CO bond of ketene, followed by a spontaneous [1,3]-rearrangement of transient vinylidene-substituted bicyclic nitrosoacetals. DFT calculations of the mechanism suggest that the [1,3]-O,C-shift proceeds through a recyclization of a biradical intermediate formed by an unusually mild homolytic cleavage of the N–O bond. The resulting products can be utilized as precursors of other fused 1,2-oxazines derivatives, in particular 1,2-oxazino-1,2,4-triazin-3-ones.

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“…56 with 53 a , 54 , 55 ) . The latter trend turned out to be general for the addition of other amines, exemplified by N ‐TBS pyrrolidine in Scheme . As in many previous cases low‐temperature NMR perfectly fitted in resolving the issue.…”

Section: Synthesis Of Nitroso Acetals Oximes and Their Derivatives Vmentioning

confidence: 99%