Novel Schiff base dimerization reaction. Interconversions involving the 3,4-dihydro-5H-2-benzazepine and 3,4,10,11-dibenzo-1,8-diazacyclotetradeca-1,3,8,10-tetraene ring systems

Goldman, Irving M.; Larson, Jerry K.; Tretter, James R.; Andrews, Edmund G.

doi:10.1021/ja01045a071

Cited by 30 publications

(7 citation statements)

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“…It crystallizes centrosymmetrically, forming an approximate rectangle with (R*,S*) configuration, as observed in the corresponding seven-membered ring 6a. Acid-catalyzed equilibria between dimers and monomers of 4,5-dihydrobenzo [c]azepines have been reported previously by Goldman et al [20] Figure 3. Molecular structure of the macrocycle 8 in the solid state (X-ray diffraction) Using low-temperature 1 H NMR techniques (600 MHz), we were able to investigate the ring-closure reaction of the imine derivative (E,Z)-4b directly.…”

Section: Methodssupporting

confidence: 56%

4,5‐Dihydro‐3H‐benzo[c]azepines from 1,7‐Electrocyclization Reactions of 2‐Aza‐4,5‐benzoheptatrienyllithium Compounds

Gerdes¹,

Sagar²,

Fröhlich³

et al. 2004

Eur J Org Chem

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Various differently substituted (2‐alkenylbenzylidene)amines 4b−d gave, upon deprotonation with amide bases and addition of an electrophile, the respective 4,5‐dihydro‐3H‐benzo[c]azepines 6a−k in moderate to good yields. The imines 4 are easily accessible from 2‐bromobenzaldehyde (1) by Wittig olefination, formylation with DMF, and subsequent condensation with benzylamine. The ring‐closure reaction is interpreted as an anionic 1,7‐electrocyclization reaction involving benzo‐annulated 2‐azaheptatrienyllithium compounds. This reaction, and the subsequent addition of the electrophiles, proceed with excellent diastereoselectivity, determined by the (E) or (Z) configuration of the imines 4b−d. The corresponding allylimines 4e,f do not give ninemembered heterocycles 7, but rather the corresponding 3‐vinyl‐4,5‐dihydro‐3H‐benzo[c]azepines 6l,m. Molecular structures of several compounds 6 in the solid state were determined by X‐ray crystallography, including the structure of a 14‐membered ring dimer 8. High‐level quantum chemical calculations on model anions concerning structures and relative energies of possible intermediates and transition states support the pericyclic mechanism suggested for the ring‐closure reaction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Section: Methodssupporting

confidence: 56%

4,5‐Dihydro‐3H‐benzo[c]azepines from 1,7‐Electrocyclization Reactions of 2‐Aza‐4,5‐benzoheptatrienyllithium Compounds

Gerdes¹,

Sagar²,

Fröhlich³

et al. 2004

Eur J Org Chem

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“…1.60 (b, 0.3 H20), 1.97 (t, 8 H, Vrh = 5.1 Hz, C-CHZ-C), 3.26 (t, 8 H, VHh = 5.1 Hz, -CH2-), 3.55 (t, 8 , 3/hh = 5.1 Hz, -CH2-), 5.59 (m, 4 H, Ar H), 6.65 (m, 4 H, Ar H), 7.15 (m, 4 H, Ar H), 7.25 (m, 4 H, Ar ), 8.20 (s, 4 H, ArCH=N), 9). A mixture of the tetraimine 8 (5.0 g, 7.8 mmol) and Na(CN)BH3 (3.9 g, 62.0 mmol) was treated with a mixture of anhydrous acetic acid-methanol (1:1, 500 mL).…”

Section: Nmrmentioning

confidence: 99%

“…13C NMR: <5 29. (5). Pure 4 (5.0 g) was mixed with Na(CN)-BH3 (3.92 g) and treated with anhydrous acetic acid-methanol (1:1, 500 mL) to produce a clear yellow solution.…”

Section: Nmrmentioning

confidence: 99%

See 1 more Smart Citation

Acid-Catalyzed Rearrangements between Cyclic Oligomers of 3,4-Dihydro-2H-1,5-benzodiazocine. Crystal and Molecular Structures of Mono- and Dinuclear Copper(II) Complexes of Tetraaza (16-Membered), Hexaaza (24-Membered), and Octaaza (32-Membered) Macrocycles

Gugger¹,

Hockless²,

Swiegers³

et al. 1994

Inorg. Chem.

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In chloroform 8 rearranges into an equilibrium mixture of the 16-membered cyclic tetraaza-diimine 5,7,8,16,-17,18-pentahydrodibenzo[g,o][ 1,5,9,13]tetraazacyclotetradecine (4) and the 24-membered hexaaza-triimine 7,8,-16,17,18,27,28-heptahydrotribenzo[g,o,w][l,5,9,13]hexaazacyclotetracosine (6). The macrocycle 4 was separated as its nickel(II) thiocyanate derivative and subsequently displaced with cyanide. Reduction of 4 with cyanoborohydride afforded the 16-membered tetraaza-tetraamine 7,8,9,10,16,17,18,19,20-nonahydrodibenzo-[g,o][ 1,5,9,13]tetrazacyclotetradecine (5). The hexaaza-triimine 6 was trapped by precipitation, isolated by fractional crystallization, and subsequently converted into the 24-membered hexaaza-

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“…Unlike the 5-merobered cyclic imine. the 7-membered ring can be expected to be reasonably stable, for the benzene analogs are known (Goldman et al, 1969).…”

Section: Chromium Trioxide Methodsmentioning

confidence: 99%

Simulation of the active site of vitamin B6-dependent enzymes

Fisher

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Novel Schiff base dimerization reaction. Interconversions involving the 3,4-dihydro-5H-2-benzazepine and 3,4,10,11-dibenzo-1,8-diazacyclotetradeca-1,3,8,10-tetraene ring systems

Cited by 30 publications

References 0 publications

4,5‐Dihydro‐3H‐benzo[c]azepines from 1,7‐Electrocyclization Reactions of 2‐Aza‐4,5‐benzoheptatrienyllithium Compounds

4,5‐Dihydro‐3H‐benzo[c]azepines from 1,7‐Electrocyclization Reactions of 2‐Aza‐4,5‐benzoheptatrienyllithium Compounds

Acid-Catalyzed Rearrangements between Cyclic Oligomers of 3,4-Dihydro-2H-1,5-benzodiazocine. Crystal and Molecular Structures of Mono- and Dinuclear Copper(II) Complexes of Tetraaza (16-Membered), Hexaaza (24-Membered), and Octaaza (32-Membered) Macrocycles

Simulation of the active site of vitamin B6-dependent enzymes

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