New Benzomorphan Ring Closure in the Synthesis of 5-Phenylbenzomorphans

Walker, Gordon N.; Alkalay, David

doi:10.1021/jo01344a054

Cited by 14 publications

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“…Reduction of the two epimers l a and l c with lithium aluminium hydride in dimethoxyethane gave the epimeric aminoalcohols 2a and 2c respectively. Other solvents (see Experimental) were markedly inferior for these reductions in accordance with experience in the preparation of 8-hydroxy-5-phenylbenzomorphan derivatives (9). The infrared (i.r.)…”

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confidence: 64%

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Transannular reactions in the dibenzo[a,d]cycloheptene series. III. Preparation of 11-substituted-10,11-dihydro-10,5-(iminomethano)-5H-dibenzo[a,d]cycloheptenes

Dobson¹,

Davis²,

Hartung³

1968

Can. J. Chem.

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Treatment of the SJJII-epoxyaniide 3 with either aninioniuni hydroxide or sodium hydride gives 10,lldihydro-miti-1 l-hydroxy-lO,5-(iniinometl1ano)-5H-dibenzo[a,cl]cyclol1epten-l3-one (In). This compound is rcadily converted to the SJ~II-epimer l c by oxidation to 10 and subsequent hydrogenation. The ketone l b reacts with Grignard reagents to give the tertiary alcohols lk,l which undergo hydrogenolysis to give the 11-substituted lactains lq,r. Reduction of the lactams with lithiuiii aluniinium hydride gives the corresponding aniines.Canadian Journal of Chemistry, 46, 3391 (1968) We have recently described the preparation of a number of l0,ll-dihydro-l0,5-(epoxymethano)-5H-dibenzo[a,d]cyclohepten-13-ones (1, 2). The present paper outlines a general route to 11-substituted-l0,ll-dihydro-l0,5-(iminometha110)-5H-dibenzo[a,d]cycloheptene derivatives 1 and 2. A different approach has been used by other workers (3-6) to prepare other derivatives and the ring system has been shown to occur naturally in the alkaloids amurensine, amurensinine, and roemfrine (7,8).We have previously found that the synepoxyamide 3 reacts with secondary amines to give anti-1 1-dialkylaminolactones. In attempts to prepare the unsubstituted anti-11-aminolactone 4a both the syn-epoxyamide 3 and the broinolactone 40 were treated with ammonium hydroxide at 140". The product, obtained in 70% yield in both cases, was not the expected lactone but the anti-1 1-hydroxylactam la. Oxidation of l a gave the ketolactam 10 which regenerated l a upon reduction with sodium borohydride. In contrast, catalytic hydrogenation of 10 gave a mixture of 20 % l a and 80 "/,f the syn-hydroxylactam Ic. This hydrogenation parallels that of the ketolactone 4c which gives the syn-hydroxylactone 4d as the major product (2). Reduction of the two epimers l a and l c with lithium aluminium hydride in dimethoxyethane gave the epimeric aminoalcohols 2a and 2c respectively. Other solvents (see Experimental) were markedly inferior for these reductions in accordance with experience in the preparation of 8-hydroxy-5-phenylbenzomorphan derivatives (9). The infrared (i.r.) hydroxyl absorptions of 2a and 2c were concentration-dependent, and concentration-independent respectively, indicating that 2a was the anti-epimer and that 2c was the syn-epimer (10). These assignments were confirmed by the reaction of the syn-aminoalcohol 2c with phosgene. The product was the cyclic carbamate 5, the structure of which was fully supported by its analytical and spectral properties. The geometry of 2a and 2c, as shown by inspection of molecular models, indicates that only 2c can form 5. Cristol and Bly (1 1) have cited an analogous cyclic carbonate formation as a structure proof of dibenzobicyclo [3.2. I Ioctadiene-exo-4-syn-8-diol. In accord with these assignments only intractable mixtures were obtained when 2a was treated with either phosgene or diethyl oxalate (12). Can. J. Chem. Downloaded from www.nrcresearchpress.com by 54.245.55.244 on 05/10/18For personal use only.

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confidence: 64%

“…Similar hydrogenolyses of the carbinols l k , l gave lq,r. Catalytic hydrogenolyses of l a and l k were unsi~ccessful, as is the case with similarly substituted benzylic alcohols (9).…”

mentioning

confidence: 95%

Transannular reactions in the dibenzo[a,d]cycloheptene series. III. Preparation of 11-substituted-10,11-dihydro-10,5-(iminomethano)-5H-dibenzo[a,d]cycloheptenes

Dobson¹,

Davis²,

Hartung³

1968

Can. J. Chem.

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“…203 and 266 nm (E 13 400 and 3 900); 6, m,ArH), 6.44 (1 H, d, [wffs], J 5 Hz), 5.96 (1 H, dd [wffs], J 9 and 5 Hz), 5.67 (1 H, dd [wffs], J 9 and 5.5 Hz), 3.55 (1 H, d [wffs], J5.5 Hz), 2.43 (1 H, d, J2. 5 Hz, C S H ) , and 2.39 (3 H, br s, Me); m/z 180, 165, 152, and 115 (35, 100,9, and 9%).…”

Section: -Methyl-5h-benzocycloheptene-5-carbonitrilementioning

confidence: 99%

Relative migratory aptitudes of doubly and triply bonded groups in a cycloheptatriene system

Battye¹,

Jones²

1986

J. Chem. Soc., Perkin Trans. 1

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I n cyclopentadiene systems, 1,5-shift of triply bonded groups is much slower than that of doubly bonded groups, whereas in the cycloheptatriene systems (34) and (29), as well as in (21 ) and (1 9), CN and CHO groups have very similar migratory tendencies. In compound (31) the CECCOPh group migrates to give (38; X = CrCCOPh, Y = H) at 60 "C, whilst the related olefin (20) fails to rearrange at 80 "C, and undergoes intramolecular Diels-Alder reaction to afford tetracycle (40) at 1 00 "C. The simple acetylene

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“…After 15 min, the oil rapidly discoloured and eventually crystallised, to yield 5,6,7,8-tetrahydro-3-methoxy-5-methyl-5,8methano-9H-benzocycloheptene-9,10-dione (17; R = OMe) (1.05 g, 67%), identified by comparison with a genuine sample (m.p., t.l.c., i.r.). 6,7,8,.-(a) 5,6,7,methoxy-5-methyl-5,8-methano benzocycloheptene-9,lO-dione (17; R = OMe) (200 mg, 0.87 mmol) and dil. aqueous sodium hydroxide (2% w/v; 19 cm3) were stirred at room temperature for 1 h until all material had dissolved.…”

Section: -Acetamidomethylmentioning

confidence: 99%

Bridged-ring nitrogen compounds. Part 7. Synthesis of the 1,4-ethano-3-benzazepine ring system

Sedgeworth¹,

Proctor²

1985

J. Chem. Soc., Perkin Trans. 1

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New Benzomorphan Ring Closure in the Synthesis of 5-Phenylbenzomorphans

Cited by 14 publications

References 0 publications

Transannular reactions in the dibenzo[a,d]cycloheptene series. III. Preparation of 11-substituted-10,11-dihydro-10,5-(iminomethano)-5H-dibenzo[a,d]cycloheptenes

Transannular reactions in the dibenzo[a,d]cycloheptene series. III. Preparation of 11-substituted-10,11-dihydro-10,5-(iminomethano)-5H-dibenzo[a,d]cycloheptenes

Relative migratory aptitudes of doubly and triply bonded groups in a cycloheptatriene system

Bridged-ring nitrogen compounds. Part 7. Synthesis of the 1,4-ethano-3-benzazepine ring system

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