Efficient total synthesis of AI-77-B, A gastroprotective substance from bacillus pumilus AI-77》.pdfVIP

TetrahedronVol 47. No 40. pp 8635-8652.1991 00404020191 $3 00+ 00 PmtcdIIIGreatBntam @ 1991h8m.X hW PlC Efficient Total Synthesis of AI-77-B, A Gastroprotective Substance from Bacillus pumilus AI-77U Yasumasa Hamada,* Osamu Hara, Akiyoshi Kawai, Yasushi Kohno, and Takayuki Shioiri* Facultyof Pharmaceutd Sciences, Nagoya City Umverslty Tanabedon, tiuho-ku, Nagoya467,Japan (Received tn UK 5 August 1991) y WO M-77-B,dlhydromoumarm. hydmxy ammo acid, StereoSekctiVeOsmytatm, mnmkdfu hm ~tm Abstract Fwst totalsyntheses of AK%0 (I), a gastroprotecttve substancefrom Bacillus pwmlus AI-77, was achieved WIa stereoselecnve and convergent manner In tks syntheses.the dthyotsocoumartnpart 2 was constructed tn one step through I)-adaitron of the benzylacanwn 17b to Boc-L-leucmal7b The hydroxy ammo actd 4 was elaboratedfrom (R)-glutamtc and m a highly stereoselectwe manner Condensatwn of2*HCl and 4, rntramolecular Pinner reacnon. followed by mdd hydrolysts@ordedAl-77-B (I) AI-77’4 were isolated as the hydrolsocoumarm anahoucs with charactensttc fluorecense from a cultured broth of B~~chspmlus AI-77 UI 1982 The stereostructure of the mayor product AI-77-B (1) was determmed by means of X-ray crystallographic analysis together with chemical degradation stues and revealed to consist of a hydroxy ammo acid and a