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. 2021 Jul 2;86(13):8955-8969.
doi: 10.1021/acs.joc.1c00884. Epub 2021 Jun 23.

Base-Catalyzed, Solvent-Free Synthesis of Rigid V-Shaped Epoxydibenzo[ b, f][1,5]diazocines

Michał Michalak  1 , Bartosz Bisek  1 , Michał Nowacki  1 , Marcin Górecki  1
Affiliations

Base-Catalyzed, Solvent-Free Synthesis of Rigid V-Shaped Epoxydibenzo[ b, f][1,5]diazocines

Michał Michalak et al. J Org Chem. .

Abstract

A novel method for the synthesis of epoxydibenzo[b,f][1,5]diazocines exhibiting a V-shaped molecular architecture is reported. The unique approach is based on unprecedented base-catalyzed, solvent-free autocondensation and cross-condensation of fluorinated o-aminophenones. The structure of the newly synthesized diazocines was confirmed independently by X-ray analysis and chiroptical methods. The rigidity of the diazocine scaffold allowed for the separation of the racemate into single enantiomers that proved to be thermally stable up to 140 °C. Furthermore, the inertness of the diazocine scaffold was demonstrated by performing a series of typical transformations, including transition metal-catalyzed reactions, proceeding without affecting the bis-hemiaminal subunit.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Examples of Rigid Molecules with V-Shaped Geometry
Scheme 2
Scheme 2. 1,1,3,3-Tetramethylguanidine (TMG)-Catalyzed Solvent-Free Autocondensation of Aminophenones
For 16 h at 120 °C. For 48 h at 120 °C. For 16 h at 80 °C.
Scheme 3
Scheme 3. TMG-Catalyzed Solvent-Free Cross-condensation of Aminophenones
For 48 h at 120 °C. For 16 h at 120 °C.
Scheme 4
Scheme 4. Postformation Modification of the Diazocine Core (TBD = 1,5,7-triazabicyclo[4.4.0]dec-5-ene)
Isolated yield after chromatography. Isolated yield after precipitation from the reaction mixture.
Scheme 5
Scheme 5. (A) Separation of Racemic (±)-2a, (B) Comparison of Experimental and Calculated ECD and UV Data, and (C) VCD and IR Spectra of Enantiomers of 2a
The calculations of the ECD and UV spectra were carried out at the CAM-B3LYP/def2-TZVP/PCM/CH3CN level of theory, while the VCD and IR spectra were calculated at the ωB97X-D/6-311+G(d,p)/ PCM/CH3CN level. More experimental and calculation details are provided in the Supporting Information. The inset in part B shows the geometry of the calculated structure of (+)-2a.
See this image and copyright information in PMC

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