87554-71-0

Upstream product

• 174393-34-1 (+/-)-verbacine 
• 87499-90-9 (E)-4-Ethoxy-1,5,9-triaza-cyclotridec-4-ene-1,9-dicarboxylic acid 1-tert-butyl ester 9-(2,2,2-trichloro-ethyl) ester 
• 84877-90-7 (E)-4-Methoxy-1,5,9-triaza-cyclotridec-4-ene-1,9-dicarboxylic acid 1-tert-butyl ester 9-(2,2,2-trichloro-ethyl) ester 
• 5661-55-2 4-phenylazetidin-2-one 
• 2216-94-6 phenylpropynoic acid ethyl ester 
• 102-92-1 Cinnamoyl chloride 
• 71-44-3 Spermine 
• 174320-09-3 ethyl (+/-)-3-{[3-({4-[(3-aminopropyl)amino]butyl}amino)propyl]amino}-3-phenylpropanoate 
• 174320-11-7 (+/-)-8-phenyl-1,5,9,13-tetraazacycloheptadecan-6-one 
• 84877-90-7 4-methoxy-1,5,9-triazacyclotridec-4-ene-1,9-dicarboxylic acid 1-tert-butyl ester 9-(2,2,2-trichloroethyl) ester 
• 87499-90-9 4-ethoxy-1,5,9-triazacyclotridec-4-ene-1,9-dicarboxylic acid 1-tert-butyl ester 9-(2,2,2-trichloroethyl) ester 
• 84877-96-3 5-[3-(1,3-Dioxo-1,3-dihydro-isoindol-2-yl)-propyl]-4-oxo-[1,5]diazonane-1-carboxylic acid tert-butyl ester 
• 84877-97-4 5-(3-Amino-propyl)-4-oxo-[1,5]diazonane-1-carboxylic acid tert-butyl ester 
• 84877-98-5 4-oxo-1,5,9-triazacyclotridecane-1-carboxylic acid tert-butyl ester 

Relevant academic research and scientific papers

β-lactams as building blocks in the synthesis of macrocyclic spermine and spermidine alkaloids

Syntheses of the macrocyclic spermidine alkaloids (±)-celacinnine (1) and (±)-dihydroperiphylline (2) as well as the related spermine alkaloid (±)-verbascenine (3) were accomplished by means of sequential ring expansions of smaller lactam rings. Three ring expansion methods were employed: (1) transamidation of N-(aminoalkyl)lactams, (2) β-lactam-lactim ether condensation followed by reductive cleavage of the bicyclic 4-oxotetrahydropyrimidine product with NaBH3CN/AcOH and (3) bicyclic acyl hydrazine formation followed by N-N bond cleavage with Na/NH3. Each synthesis features ring expansion of a 4-phenylazetidin-2-one intermediate that undergoes transamidative ring expansion or lactim ether condensation.

Metal-Templated Macrolactamization of Triamino and Tetramino Esters. Facile Synthesis of Macrocyclic Spermidine and Spermine Alkaloids, (S)-(+)-Dihydroperiphylline, (±)-Buchnerine, (±)-Verbacine, (±)-Verbaskine, and (±)-Verbascenine

The total synthesis of spermidine and spermine alkaloids. (S)-(+)-dihydroperiphylline (1), (±)-buchnerine (2), (±)-verbacine (3), (±)-verbaskine (4), and (±)-verbascenine (5), is described. The construction of macrocyclic lactams has been efficiently accomplished by the metal-templated cyclization of triamino esters and tetraamino esters. It was also found that the antimony(III) ethoxide is useful as an intermolecular amidation catalyst.

Verballoscenine, the Z isomer of verbascenine from Verbascum phoeniceum

The Z isomer (13-acetyl-1-(Z)-cinnamoyl-6-oxo-8-phenyl-1,5,9,13- tetraazacycloheptadecane; verballoscenine) of the 17-membered macrocyclic lactam alkaloid verbascenine was isolated from Verbascum phoeniceum and structurally characterized. The presence in the same plant material of the analogous N-13 nonacetyl alkaloids verbacine and verballocine as precursors in the biogenesis of verbascenine and verbascenine is reported.

NEW APPROACHES TO THE SYNTHESIS OF SPERMINE AND SPERMIDINE ALKALOIDS

New approaches to the formation of macrocyclic lactams are described involving successive ring expansion of 8-lactams and other heterocyclic systems.These methods have been used in the synthesis of a number of spermine and spermidine alkaloids including homaline, celacinnine, dihydroperiphylline, chaenorhine and verbascenine.