180324-13-4

Upstream product

• 180324-14-5 (S)-4-phenyl-1-(2'-cyanoethyl)-1,5-diazacyclononan-2-one 
• 163460-82-0 tert-butyl (E)-[(R)-p-tolylsulfinyl]cinnamate 
• 163460-81-9 tert-butyl (E)-[(S)-p-tolylsulfinyl]cinnamate 
• 3646-50-2 3-Amino-3-phenylpropionic acid 
• 37088-66-7 (3S)-methyl 3-amino-3-phenylpropanoate 
• 112020-24-3 (+)-(2S)-2,6,7,8-tetrahydro-2-phenyl-3H-pyrrolo<1,2-a>pyrimidin-4-one 
• 100-52-7 benzaldehyde 
• 112020-25-4 (S)-4-phenyl-1,5-diazacyclononan-2-one 
• 76598-25-9 (R)-(+)-1,5-Diaza-4-phenylbicyclo<4.3.0>nonan-2-one 
• 400782-35-6 (S)-(-)-4-phenyl-1-(3'-phthalimidopropyl)-1,5-diazacyclononan-2-one 

Downstream Products

• 166373-40-6 (-)-(2S)-2-phenyl-1,5,9-triazacyclotridecan-4-one 
• 53938-05-9 (S)-(-)-celacinnine 
• 74133-16-7 (-)-(2S)-9-hydroxy-2-phenyl-1,5,9-triazacyclotridecan-4-one 

Relevant academic research and scientific papers

Conjugate addition of 6-membered hydrazine to chiral tert-butyl (E)-2-(p-tolylsulfinyl)cinnamates. Synthesis of (S)-celacinnine

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

(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.

95. Asymmetric synthesis of the alkaloids mayfoline and N(1)-Acetyl-N(1)-deoxymayfoline

The total syntheses of the spermidine alkaloids (-)-mayfoline (11) and (+)-N(1)-acetyl-N(1)-deoxymayfoline (12) are described. These macrocyclic lactams belong to the most interesting conjugates of the polyamine derivatives very commonly found in nature. The enantioselective syntheses were achieved through resolution of the methyl 3-amino-3-phenylpropanoate (2) by recrystallization of its (+)-L-tartrate salt. Construction of the 13-membered ring ensued through condensation, reductive ring expansion (internal bond cleavage), and finally a transamidation reaction involving a second ring expansion.

ASYMMETRIC SYNTHESIS OF CELACINNINE UTILIZING OPTICALLY ACTIVE VINYL SULFOXIDES

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).