88931-11-7

Upstream product

• 1393593-38-8 (4S,αR)-4-phenyl-N(5)-(α-methylbenzyl)-1,5-diazocan-2-one 
• 1393593-37-7 methyl (3S, αR)-3-[N-( 3'-aminopropyl)-N-(α-methylbenzyl)amino]-3-phenylpropanoate 
• 1393593-36-6 methyl (3S, αR)-3-[N-( 3'-azidopropyl)-N-(α-methylbenzyl)amino]-3-phenylpropanoate 
• 1393593-35-5 methyl (3S, αR)-3-[N-( 3'-chloropropyl)-N-(α-methylbenzyl)amino]-3-phenylpropanoate 
• 1356849-80-3 methyl (3S,αR)-3-[N-( 3'-chloropropyl)-N-(α-methyl-4''-methoxybenzyl)amino]-3-phenylpropanoate 
• 37088-64-5 (S)-4-phenyl-2-azetidinone 
• 614-19-7 (S)-3-amino-3-phenylpropanoic acid 
• 400782-36-7 t-butyl (+)-3-hydroxy-3-phenyl-2-<(R)-p-tolylsulfinyl>propionate 
• 400782-30-1 t-butyl (-)-3-hydroxy-3-phenyl-2-<(S)-p-tolylsulfinyl>propionate 
• 163460-81-9 tert-butyl (E)-[(S)-p-tolylsulfinyl]cinnamate 
• 163460-82-0 tert-butyl (E)-[(R)-p-tolylsulfinyl]cinnamate 
• 173313-22-9 (S)-(-)-4-phenyl-1,5-diazabicyclo<3.3.1>octan-2-one 
• 173313-23-0 (R)-(+)-4-phenyl-1,5-diazabicyclo<3.3.1>octan-2-one 
• 153221-67-1 (S)-N-(3-chloropropyl)-4-phenylazetidin-2-one 

Downstream Products

• 88931-13-9 (S,S)-1,4-di-[2'-oxo-4'-phenyl-N(5')-methyl-1',5'-diazocan-N(1')-yl]butane 
• 82359-84-0 1,4-bis<(S)-(-)-2-oxo-4-phenyl-1,5-diazacyclooctanyl>-butane 
• 32975-62-5 (S)-(+)-5-methyl-4-phenyl-1,5-diazacyclooctan-2-one 
• 173398-08-8 (R)-(-)-5-methyl-4-phenyl-1,5-diazacyclooctan-2-one 
• 20410-93-9 1,1'-(butane-1,4-diyl)bis[hexahydro-5-methyl-4-phenyl-1,5-diazocin-2(1H)-one] 

Relevant academic research and scientific papers

Asymmetric syntheses of the homalium alkaloids (-)-(S, S)-homaline and (-)-(R, R)-hopromine

The highly diastereoselective conjugate additions of the novel lithium amide reagents lithium (R)-N-(3-chloropropyl)-N-(α-methylbenzyl)amide and lithium (R)-N-(3-chloropropyl)-N-(α-methyl-p-methoxybenzyl)amide to α,β-unsaturated esters were used as the key steps in syntheses of the homalium alkaloids (-)-(S,S)-homaline and (-)-(R,R)-hopromine. The asymmetric synthesis of (-)-(S,S)-homaline was achieved in 8 steps and 18% overall yield, and the asymmetric synthesis of (-)-(R,R)-hopromine was achieved in 9 steps and 23% overall yield, from commercially available starting materials in each case. These syntheses therefore represent by far the most efficient total asymmetric syntheses of these alkaloids reported to date. A sample of the (4′R,4′′S)-epimer of hopromine was also produced using this approach, which provided the first unambiguous confirmation of its absolute configuration and therefore that of natural (-)-(R,R)-hopromine.

Asymmetric synthesis of 4-phenyl-1,5-diazacyclooctan-2-one using optically active vinyl sulfoxides

Both enantiomers of (S)- and (R)-4-phenyl-1,5-diazacyclooctan-2-ones (7) were synthesized stereoselectively with good optical purity by the asymmetric conjugate addition of pyrazolidine to optically active vinyl sulfoxides, t-butyl (E)-2-[(R)- and (S)-p-tolylsulfinyl]cinnamates, respectively. Starting from 7, a synthesis of optically active homaline was achieved.

Synthesis of the Alkaloid Homaline in (+/-) and Natural (S,S)-(-) Forms, using Amination and Transamidative Ring Expansion in Liquid Ammonia

Synthesis of the alkaloid homaline in (+/-) and natural (S,S)-(-) forms is reported.Linking of 2-azacyclooctanone units either directly or successively using 1,4-dihalogenobutanes or 1,4-dihalogenobut-2-ynes is examined. (+/-)-5-Methyl-4-phenyl-1,5-diazacyclooctan-2-one is first made by a 2,2'-dithiodipyridine/triphenylphosphine-mediated cyclisation, and then by amination and transamidative ring expansion from N-(3-chloropropyl)-4-phenylazetidin-2-one in liquid ammonia, followed by N-methylation.Coupling through a 1,4-dihalogenobutane of either the N-methylated azalactam, or the unmethylated azalactam followed by methylation, gave homaline in (+/-) and meso forms. (R)-(-)-Phenylglycine was converted via (S)-β-phenyl-β-alanine into an (S)-β-lactam which was then alkylated with 1-bromo-3-chloropropane, and aminated and ring expanded in liquid ammonia.Coupling of the homochiral azalactam (2 mol) so formed with 1,4-dibromobutane, followed by N-methylation, gave (S,S)-(-)-homaline identical with the natural material.