Asymmetric Total Synthesis of Pinnaic Acid

Abstract

Zusammengebastelt: Die asymmetrische Totalsynthese von Pinnasäure gelang auf einem stereospezifischen Weg, wobei Schlüsselschritte eine Pd‐katalysierte Trimethylenmethan(TMM)‐[3+2]‐Cyclisierung, eine vierstufige Tandem‐Hydrierung‐Cyclisierung und Kreuz‐Olefinmetathesereaktionen waren (siehe Schema).

In an Attempt to Provide a User's Guide to the Galaxy of Benzylidene, Alkoxybenzylidene, and Indenylidene Ruthenium Olefin Metathesis Catalysts

“…Since in many published syntheses 10-30 mol % or more of Ru has been used as a default minimal amount, [12] we think that this observation is of great practical value. [16] The first-generation catalysts can still be used as a more economical alternative for metathesis reactions in which dior trisubstituted C=C bonds are formed. [1,12] In some reactions, it has been observed that first-generation catalysts are more selective as compared with their second-generation heirs.…”

Asymmetric total synthesis strategies of halichlorine and pinnaic acid

“…In 2007, Uemura's group completed the asymmetric total synthesis of pinnaic acid. 36 Then, they continued this route and completed the enantioselective total synthesis of halichlorine based on early result. In this section, we give a detailed report on this total synthesis route of (+)-halichlorine (Scheme 14).…”

“…In 2007, the Uemura group described a novel strategy for asymmetric total synthesis using Pd-catalyzed trimethylenemethane [3 + 2] cyclization (Pd-TMM cyclization). 36 In 2014, they further optimized this route, which achieved total synthesis of pinnaic acid. 37 Aldehydes were formed by Parkin-Doering oxidation (SO 3 $Py, DMSO) from the key intermediate 14.8 and reacted with phosphonate 25.1 (Horner-Wadsworth-Emmons reaction).…”

“…In 2007, the Uemura group described a novel strategy for asymmetric total synthesis using Pd-catalyzed trimethylenemethane [3 + 2] cyclization (Pd-TMM cyclization). 36 In 2014, they further optimized this route, which achieved total synthesis of pinnaic acid. 37…”

Modular Asymmetric Synthesis of Functionalized Azaspirocycles Based on the Sulfoximine Auxiliary

“…10,11 In 2004, HEATHCOCK and co-workers reported the total synthesis of the racemates of 4 and 7. 12 Later some other groups published formal total syntheses of these marine alkaloids.…”