Total Synthesis of Avrainvillamide (CJ-17,665) and Stephacidin B

✍ Scribed by Phil S. Baran; Carlos A. Guerrero; Benjamin D. Hafensteiner; Narendra B. Ambhaikar

• Publisher: John Wiley and Sons
• Year: 2005
• Tongue: English
• Weight: 318 KB
• Volume: 117
• Category: Article
• ISSN: 0044-8249
• DOI: 10.1002/ange.200500655

✦ Synopsis

Scheme 3. Synthesis of simple avrainvillamide model 15 and the successful conversion of (+)-1 into (+)-3 and (À)-2. Reagents and conditions: a) NaBH 3 CN (10 equiv), AcOH, 25 8C, 12 h, 53 %; b) Na 2 WO 4 •2 H 2 O (0.2 equiv), aq. 35 % H 2 O 2 (50 equiv), MeOH, H 2 O, 25 8C, 6 h, ca. 30 %; c) NaBH 3 CN (50 equiv), AcOH, 25 8C, 24 h, 93 %; d) SeO 2 (0.25 equiv), 35 % H 2 O 2 (50 equiv), dioxane, 25 8C, 40 h, 27 % 3 with 50 % recovered 16; e) Procedure A: Preparative TLC (SiO 2 , EtOAc); Procedure B: [6] Et 3 N (excess), CH 3 CN, 25 8C, 1 h; Procedure C: DMSO, then solvent removal, approx. 2:1 mixture of 3 to 2, purified by preparative TLC. PMB = p-methoxybenzyl; DMSO = dimethyl sulfoxide.