Synthesis of Tetracyclic 2,3-Dihydro-1,3-diazepines from a Dinitrodibenzothiophene Derivative

Abstract

Triply-fused 1,3-diazepine derivatives have been obtained by acidic reduction of rotationally locked and sterically hindered nitro groups in the presence of an aldehyde or ketone. The nitro groups are sited on adjacent rings of a dicyanodibenzothiophene-5,5dioxide which also displays fully reversible two-electron accepting behavior. The synthesis, crystallographically determined molecular structures and aspects of the electronic properties of these new molecules are presented. Developing new routes to underexplored heterocyclic motifs is a fundamental driving force in organic chemistry and is essential to identifying new structures of medicinal or technological value. Diazepines are of major pharmaceutical importance. 1-3 1,2-and 1,4-benzodiazepines in

1,3‐Diazepine Derivatives: Strategies for Synthesis

“…Due to difficulty in isolating diamine intermediate 78, reaction was done in one pot with yields ranging 39 % to 45 % (Scheme 20). [35] Scheme 16. Synthesis of DMP323, an HIV protease inhibitor.…”

“…of sodium methoxide, targeted diazepines 98 a-c were obtained Scheme 20. Synthesis of tetracyclic 1,3-diazepines 79 a-c. [35] Scheme 21. Synthesis of dibenzo-ou dipyrido [1,3]diazepines 83.…”

2,2′‐Bis(arylamino)‐1,1′‐biaryls as Building Blocks for the Synthesis of Dibenzo[d,f][1,3]diazepines, Dibenzo[d,f][1,3]diazepinones, and Dibenzo[c,e][1,2,7]thiadiazepine 6‐Oxides

“…Although already described in 1929 by Le Fèvre, [11] only limited reports for the construction of 1,3‐diazepines are known. Despite considerable recent synthetic efforts in this area, [1d,3a,b,d,12–26] the synthesis of functionalized 1,3‐diazepine derivatives remains a challenging task. Therefore, better synthetic routes to the 1,3‐diazepine framework from readily available starting materials are desirable.…”