345349-97-5Relevant articles and documents
Asymmetric syntheses of pharmaceuticals containing a cyclopropane moiety using catalytic asymmetric Simmons-Smith reactions of allylalcohols: Syntheses of optically active tranylcypromine and milnacipran
Ishizuka, Yuki,Fujimori, Hirohisa,Noguchi, Takuya,Kawasaki, Masashi,Kishida, Mari,Nagai, Takuya,Imai, Nobuyuki,Kirihara, Masayuki
, p. 1311 - 1313 (2013/10/22)
Asymmetric synthesis of tranylcypromine was achieved using an enantioselective Simmons-Smith cyclopropanation catalyzed by a simple disulfonamide derived from an -amino acid. The optically active milnacipran was also synthesized by porcine pancreas lipase-catalyzed selective monoacylation of the C4-hydroxy group in (Z)-2-phenylbut-2-ene-1,4-diol and the enantioselective Simmons-Smith cyclopropanation as the key steps.
Synthesis of (+)- and (-)-milnaciprans and their conformationally restricted analogs
Shuto, Satoshi,Ono, Shizuka,Hase, Yukako,Kamiyama, Noriko,Matsuda, Akira
, p. 641 - 644 (2007/10/02)
Reaction of (R)-epichlorohydrin [(R)-5] and phenylacetonitrile (6) in the presence of NaNH2 in benzene gave a cyclopropane derivative which was isolated as lactone 4 [(1S,2R)-2-oxo-1-phenyl-3-oxabicyclo[3,1,0]hexane] of 96% e.e. in 67% yield, after alkaline hydrolysis of the cyano group. Compound 4 was readily converted to (+)-milnacipran [(+)-1], by which the absolute stereochemistry of (+)-1 was confirmed. (1S,2R)-1-phenyl-2-[(S)-1-aminoethyl]-cyclopropane-N,N-diethylcarboxam ides (2), a conformationally restricted analog of 1, was also synthesized in high enantiomeric purity from 4. Starting from (S)-epichlorohydrin [(S)-5], their corresponding enantiomers, namely (-)-milnacipran [(-)-1] and ent-2, were also synthesized.
