76598-25-9Relevant academic research and scientific papers
One step synthesis of optically active diazabicyclo-[3.3.0] octanones or diazabicyclo [4.3.0] nonanones by asymmetric conjugate addition of cyclic hydrazine
Seki, Chigusa,Hirama, Masafumi,Sato, Takeshi,Takeda, Saya,Kohari, Yoshihito,Ishigaki, Kazuhiro,Ohuchi, Masafumi,Yokoi, Kiyoshi,Nakano, Hiroto,Uwai, Koji,Takano, Nobuhiro,Umemura, Kazuyuki,Matsuyama, Haruo
experimental part, p. 1045 - 1052 (2012/07/28)
Asymmetric conjugate addition-cyclization of lithium amide of 6-membered hydrazine 4, piperidazine, (or 5-membered hydrazine 6, pyrazolidine) to N-(E)-cinnamoyl-(1S)-2,10-camphorsultam (1S)-3 afforded β-amino acid derivative (S)-1 {or (S)-2} for the synthesis of polyamine alkaloids in good yield with good stereoselectivity (up to 86% ee).
β-lactams as building blocks in the synthesis of macrocyclic spermine and spermidine alkaloids
Wasserman, Harry H,Matsuyama, Haruo,Robinson, Ralph P
, p. 7177 - 7190 (2007/10/03)
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.
Conjugate addition of 6-membered hydrazine to chiral tert-butyl (E)-2-(p-tolylsulfinyl)cinnamates. Synthesis of (S)-celacinnine
Matsuyama,Itoh,Matsumoto,Ohira,Hara,Yoshida,Iyoda
, p. 2924 - 2930 (2007/10/03)
Two enantiomers of the bicyclic lactam, (S)- and (R)-9-phenyl-1,6-diazabicyclo[4.3.0]nonan-7-one (6), were synthesized stereoselectively with high optical purity (95% ee) by the asymmetric conjugate addition-cyclization of piperidazine to chiral vinyl sulfoxides, tert-butyl (E)-2-[(R)- and (S)-p-tolylsulfinyl]cinnamate (4), followed by removal of the p-tolylsulfinyl group with SmI2. The subsequent reductive cleavage of the N-N bond of the bicyclic lactam 6 with sodium in liquid ammonia produced the corresponding 9-membered azalactam, (S)- and (R)-4-phenyl-1,5-diazacyclononan-2-one (7) with 99% and 97% ee, respectively. X-ray crystallography showed that (S)-7 exists exclusively as a trans conformer in the crystal state. Starting from (S)-7, naturally occurring (S)-celacinnine 1 was synthesized with 99% ee employing the ring-expansion reaction via intramolecular transamidation.
Chiral vinyl sulfoxides as useful reagents for the synthesis of β-amino acid derivatives
Matsuyama, Haruo,Itoh, Nobuhiro,Yoshida, Masato,Iyoda, Masahiko
, p. 475 - 476 (2007/10/03)
(S)- and (R)-β-amino acid derivatives were synthesized by the asymmetric conjugate addition of ammonia and piperidazine to t-butyl (E)-2-[(R)-and (S)-p-tolylsulfinyl]cinnamates, respectively.
ASYMMETRIC SYNTHESIS OF CELACINNINE UTILIZING OPTICALLY ACTIVE VINYL SULFOXIDES
Itoh, Nobuhiro,Matsuyama, Haruo,Yoshida, Masato,Kamigata, Nobumasa,Iyoda, Masahiko
, p. 415 - 418 (2007/10/02)
First asymmetric synthesis of celacinnine (10) was achieved from the nine-membered azalactam, 3-phenyl-4-azaoctanelactam (6), which was synthesized by the addition of piperidazine (4) to optically active vinyl sulfoxides (3).
Diastereoselective Conjugate Addition of Cyclic Hydrazine to Optically Active Vinyl Sulfoxide. A Novel Synthesis of Optically Active Azalactams
Matsuyama, Haruo,Itoh, Nobuhiro,Kamigata, Nobumasa
, p. 1547 - 1550 (2007/10/02)
Optically active (R)-(+)-1,5-diaza-4-phenylbicyclononan-2-one (5) was prepared in high optical purity by diastereoselective conjugate addition of piperidazine to optically active (E)-(S)-1-(methoxycarbonyl)-2-phenylvinyl p-tolyl sulfoxide, followed
NEW APPROACHES TO THE SYNTHESIS OF SPERMINE AND SPERMIDINE ALKALOIDS
Wasserman, Harry H.,Robinson, Ralph P.
, p. 279 - 288 (2007/10/02)
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.
TRANSAMIDATION REACTIONS IN THE FORMATION OF MACROCYCLIC LACTAMS. A TOTAL SYNTHESIS OF CELLACINNINE.
Wasserman, Harry H.,Robinson, Ralph P.,Matsuyama, Haruo
, p. 3493 - 3496 (2007/10/02)
The macrocyclic spermidine alkaloid, cellacinnine, has been synthetized by methods involving successive ring expansion reactions.One route starts with 4-phenyl-2-azetidinone; another, with piperidazine.
