Thermal and photochemical transformations of 1-(arylazo)-n-arylidene-2-naphthylamines

Carbocycle synthesis via novel organopalladium addition to nitriles

“…The annulation of 2iodobenzonitrile onto 1-phenyl-1-propyne resulted in the formation of an inseparable 1:1 mixture of regioisomeric indenones 3 and 4 in a combined 32% yield after a 48 h reaction period ( Table 3, entry 1). Only a trace amount of 2,3-di-n-propyl-l-indenone (5) was detected in the reaction of 4-octyne (entry 2), with about 40% of the starting 2iodobenzonitrile still present after 48 h. Indenone 6 was formed in low yield when 2iodobenzonitrile was annulated onto 4,4-dimethyl-2-pentyne (entry 3). The annulation of 2methyl-4-phenyl-3-butyn-2-ol afforded the expected indenone 7 in an 8% yield along with 3phenyl-2-(2-propenyl)-l-indenone (8), which was apparently derived from 7 (entry 4).…”

“…Thin-layer chromatography was performed using commercially prepared .87 (dd, 7 = 7.5, 1.5 Hz, IH); 13 C NMR (CDC1 3 ) 5 26.6,34.3,48.7,102.6,124.6,128.4,129.0,130.7,139.0,139.9;IR (neat) 1H), 7.85 (dd, 7 =7.5, 1.5 Hz, 1H); l3 C NMR (CDC1 3 ) Ô 16. 3,22.9,25.1,35.4,41.0,48.8,102.8,122.9,128.3,128.9,130.9,138.6,139.8;IR (neat) 31.7,36.4,45.9,102.1,124.4,128.4,128.8,129.7,139.0,139.8;IR (neat) 4,13.6,43.5,101.2,123.1,128.5,128.8,129.5,139.3,139.6;IR (neat) 5,43.5,50.7,103.1,123.1,125.9,128.0,128.2,128.9,129.1,…”

“…cat Pd (5) During the course of our study of the scope of the nitrile annulation chemistry, we have found that bicyclic alkenes undergo facile annulation by 2-iodobenzonitrile (eq 6).…”

“…Obtained in a 91% yield from the reaction of norbomene and 9-cyano-lO-iodophenanthrene 20 29.5,32.3,39.5,40.4,46.4,56.3,122.5,123.6,124.9,126.0,127.0,127.1,127.2,128.1,128.6,129.8,130.1,132.1,133.8,159.9,209.2;IR (neat) 5,28.9,31.9,40.8,41.3,48.1,55.8,132.2,136.2,158.6,205.8;IR (neat) 1716, 2870, 2949 cm 1 ; HRMS m/z 318.162625 (calcd forC^H^Oj, 318.161980). 28.7,29.1,32.7,40.8,41.3,48.2,55.9,121.7,134.8,146.3,154.3,164.9,207.8;IR (neat) 1714,2954 cm 1 ; HRMS m/z 199.09995 (calcd forC l3 Hi 3 NO, 199.099714).…”

“…3 Among many transition metals used in organic synthesis, palladium is particularly useful as it offers the most versatile possibilities for carbon-carbon bond formation. 4 Palladium reagents have been used extensively to prepare various carbo-and heterocyclic compounds, 5 both by cyclic carbopalladation and annulation. 6 One of the most important factors contributing to such widespread application of palladium catalysts is their tolerance of most important organic functional groups.…”