Photochemical synthesis of 6,7-dihydro-5H-dibenz[c,e]azepine and 5,6,7,8-tetrahydrodibenz[c,e]azocine derivatives

Jeffs, Peter W.; Hansen, John F.; Brine, George A.

doi:10.1021/jo00908a008

Cited by 27 publications

(4 citation statements)

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“…It is well-established that UV-light can allow HAS to occur in the absence of radical initiators, [29][30][31][32][33][34][35][36][37] particularly aryl radical substitutions, which can be superior to those using Bu 3 SnH. 36 Benzimidazol-2-yl radicals readily cyclize onto aromatics with best yields achieved in the presence of a small quantity of sodium carbonate required to quench HI (Scheme 9).…”

Section: Use Of Uv Lightmentioning

confidence: 99%

A new era for homolytic aromatic substitution: replacing Bu₃SnH with efficient light-induced chain reactions

Gurry

Aldabbagh

2016

Org. Biomol. Chem.

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Section: Use Of Uv Lightmentioning

confidence: 99%

A new era for homolytic aromatic substitution: replacing Bu₃SnH with efficient light-induced chain reactions

Gurry

Aldabbagh

2016

Org. Biomol. Chem.

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“…Jeffs and coworkers demonstrated [21] a photochemical synthesis for the synthesis of 6,7-dihydro-5H-dibenz[c,e]-azepine and 5,6,7,8-tetrahydrodibenz[c,e]azocine derivatives in 1975. The authors developed the outer skeleton needed for the photochemical ring closure by the reductive amination of a 2-iodobenzaldehyde derivative with the same amine in presence of a borohydride (Scheme 4).…”

Section: The Early History Of Apogalanthamine Analoguesmentioning

confidence: 99%

An Overview of Syntheses of Apogalanthamine Analogues and 7‐Aza Derivatives of Steganacin and Steganone

Appukkuttan

Eycken

2008

Eur J Org Chem

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“…Difference in chemical shifts of geminal, methylene protons of azepine ring adjoined to naphthoquinone and of azocine ring bridging biphenyl group have also been reported. 28,29) In addition, formation of azepine ring by RCM of olefin 4 was established by HMBC analysis (Fig. 5).…”

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confidence: 99%

Application of Ring-Closing Metathesis for the Synthesis of Benzo[3,4]azepino[1,2-b]isoquinolin-9-ones

Van

Khadka

et al. 2011

CHEMICAL & PHARMACEUTICAL BULLETIN

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NoteIn order to heal cancer, chemotherapeutic treatments have been investigated over the last several decades.1,2) Conformation studies and synthesis of medium-sized heterocyclic compounds, which have been investigated as the scaffolds of many biologically interesting structures, have received more attention.3-5) Recently, we studied the synthesis of 3-arylisoquinoline derivatives such as indeno [1,2-c] 10) as constrained structures through molecular modeling to find plausible antitumor agents. The diversely rigidified 3-arylisoquinoline analogs exhibited promising cytotoxicities and topoisomerase I inhibitory activities.11) We also reported the convenient synthesis of protoberberines using ring-closing metathesis (RCM) as shown in Fig. 1. 12)Seven-membered heterocyclic rings are considered attractive molecules due to the points of structural determination of natural products as well as their interesting pharmacological actions. [3][4][5] In this paper we applied RCM [13][14][15][16][17][18][19][20][21][22][23][24][25][26] for the formation of seven-membered benzo [3,4]azepino[1,2-b]isoquinolinone 5, and the retrosynthetic pathway of benzo [3,4]azepino [1,2-b]isoquinolinone 5 is depicted in Chart 1. The coupling reaction of toluamide 7 with benzonitrile 8 afforded the 3-arylisoquinolinone 6, which could be modified to diene 4 as a key intermediate for the RCM reaction.The synthetic approach of using the RCM reaction to prepare the seven-membered ring was based on the synthesis of 3-arylisoquinolines 4 that contain olefins at the appropriate positions. To synthesize the 3-arylisoquinoline 6a, a coupling reaction between N,N-diethyl-o-toluamide 7a and benzonitrile 8a was performed (Chart 2).10) Generally, the chemical yield of this reaction is low (33 to 49%) due to the unknown side product and it is quite dependent on the substitution pattern of aromatic rings of the starting materials.10) As a part of our continuous research on natural alkaloids synthesis, including biological evaluation of 3-arylisoquinolines, the coupling reaction of o-toluamides with benzonitriles was utilized to provide the desired molecules.27) Significant increases in the topoisomerase I inhibitory activities of these compounds were observed through conversion of flexible 3-aryl rings to rigid forms such as isoindolo[2,1-b]isoquinolinones, benz-[b]oxepines, 12-oxobenzo[c]phenanthridinones and indeno-[1,2-c]isoquinolines, and molecular docking studies were used to explain the potency of these compounds.11) The above coupling reaction has advantages as a synthetic tool for the construction of 3-arylisoquinolines because it is easily adaptable to starting materials with diverse aromatic ring substitutions and it is a one-pot procedure for the construction of all essential carbon atoms in the desired molecules. Cycloaddition reaction between toluamides and benzonitriles was applied to prepare the 3-arylisoquinolines, and their chemical transformation to the dienes 4 was performed. The ring-closing metathesis (RCM) reaction afforded the desir...

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Photochemical synthesis of 6,7-dihydro-5H-dibenz[c,e]azepine and 5,6,7,8-tetrahydrodibenz[c,e]azocine derivatives

Cited by 27 publications

References 3 publications

A new era for homolytic aromatic substitution: replacing Bu₃SnH with efficient light-induced chain reactions

A new era for homolytic aromatic substitution: replacing Bu₃SnH with efficient light-induced chain reactions

An Overview of Syntheses of Apogalanthamine Analogues and 7‐Aza Derivatives of Steganacin and Steganone

Application of Ring-Closing Metathesis for the Synthesis of Benzo[3,4]azepino[1,2-b]isoquinolin-9-ones

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Photochemical synthesis of 6,7-dihydro-5H-dibenz[c,e]azepine and 5,6,7,8-tetrahydrodibenz[c,e]azocine derivatives

Cited by 27 publications

References 3 publications

A new era for homolytic aromatic substitution: replacing Bu3SnH with efficient light-induced chain reactions

A new era for homolytic aromatic substitution: replacing Bu3SnH with efficient light-induced chain reactions

An Overview of Syntheses of Apogalanthamine Analogues and 7‐Aza Derivatives of Steganacin and Steganone

Application of Ring-Closing Metathesis for the Synthesis of Benzo[3,4]azepino[1,2-b]isoquinolin-9-ones

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A new era for homolytic aromatic substitution: replacing Bu₃SnH with efficient light-induced chain reactions

A new era for homolytic aromatic substitution: replacing Bu₃SnH with efficient light-induced chain reactions