C N O C A B N A B C O O D N A B O O D C PhCH CHCOCl N Ar CO 2 Et CO 2 Et Ph O N Ph O Ar CO 2 H N Ph O Ar COCHN 2 N Ph O ArNHCH(CO 2 Et) 2 Ar 2 3a,b CO 2 Me N Ph O 4a,b KOH (2 equiv.) i, SOCl 2 , benzene Ar Et 3 N, benzene reflux CO 2 H EtOH–H 2 O/reflux ii, CH 2 N 2 , ether–CH 2 Cl 2 5a,b 6a,b N O O H H Ar reflux Ag 2 O, MeOH 7a,b KOH, EtOH–H 2 O reflux PPA, 100 °C a Ar = p-chlorophenyl b Ar = m-nitrophenyl 8 1a,b + COCl N CO 2 Et CO 2 Et Ar O N HO 2 C O Ar N O Ar N 2 HC N O Ar MeO 2 C ArNHCH(CO 2 Et) 2 Et 3 N, benzene reflux i, SOCl 2 N O Ar 11a,b 9 10a,b HO 2 C 12a,b ii, CH 2 N 2 13a,b 14a,b N O Ar Ag 2 O, MeOH 2 KOH, acetone–H 2 O reflux H H KOH, EtOH O reflux reflux 15a,b PPA O 100 °C 1a,b + 80 J. CHEM. RESEARCH (S), 1997 J. Chem. Research (S), 1997, 80–81 J. Chem. Research (M), 1997, 0568–0583 Studies on -Lactams: Synthesis of some 3-Aryl- 1,3a,4,9b-tetrahydrobenzo[e]indole-2,5-dione Derivatives and its Implication in the Total Synthesis of Functionalized 17-Azasteroids Gandhi K. Kar, Dandala Ramesh, Basanta G. Chatterjee and Jayanta K. Ray* Department of Chemistry, Indian Institute of Technology, Kharagpur 721302, India The -lactam esters 3 and 10, prepared from anilinomalonates and 3-arylacryloyl chloride, are hydrolysed and selectively decarboxylated to the trans-acids 4 and 11; further homologation and cyclization produce the tri- and tetra-cyclic -lactam derivatives 8 and 15 that simulate the B-C-D/A-B-C-D ring system of many azasteroids. -Lactam moieties, fused to carbocyclic rings, are common in bioactive natural products 1,2 and consequently many syn- thetic strategies have been recorded. 3–6 We report here a novel sequence of reactions that synthesise -lactams with appropriate functionalities for further elaboration and thus construction of azasteroids (Schemes 1 and 2). Our strategy involved the construction of the -lactam moiety first, the starting materials already having rings B/A B, followed by the construction of the ring C in the final stage to achieve model and target 17-azasteroids (Fig. 1). Thus condensation of arylaminomalonates 1 with -aryl- acryloyl chlorides 2 in the presence of triethylamine exten- sively produced the -lactam diesters 3 in good yields (Scheme 1). Saponification with in situ decarboxylation of 3 with alco- holic KOH (2 equiv.) under reflux exclusively produced the trans-acid 4 in excellent yield. The structure was confirmed by spectral data (IR, NMR, MS) and elemental analysis. The trans-geometry was assigned by the coupling constants of 4-H and 5-H (J ca. 4–5 Hz). Annulation of the CO 2 H side chain was achieved by the Arndt–Eistert method. Thus the -lac- tam monoacid 4 was converted into the acid chloride with SOCl 2 and subsequent treatment of the acid chloride with diazomethane gave the diazoketone 5 in excellent yield. The *To receive any correspondence. Fig. 1 Scheme 1 Scheme 2 Published on 01 January 1997. Downloaded on 26/10/2014 18:22:29. View Article Online / Journal Homepage / Table of Contents for this issue