Synthesis of All 16 Stereoisomers of Pinesaw Fly Sex Pheromones − Tools and Tactics for Solving Problems in Fluorous Mixture Synthesis

• Published in: Journal of organic chemistry Vol. 70; no. 23; pp. 9447 - 9462
• Main Authors: Dandapani, Sivaraman, Jeske, Mario, Curran, Dennis P
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 11.11.2005; Amer Chemical Soc
• Subjects: Aliphatic compounds; Animals; Chemistry; Chemistry, Organic; Chemistry, Organic - methods; Exact sciences and technology; Female; Fluorine - chemistry; Hymenoptera - chemistry; Organic chemistry; Physical Sciences; Preparations and properties; Science & Technology; Sex Attractants - chemical synthesis; Sex Attractants - chemistry; Stereoisomerism; LIBRARIES; MICRODIPRION-PALLIPES HYMENOPTERA; ANALOGS; DIPRIONIDAE; ENANTIOMERS; CONDENSATION; SEPARATION; PURE; JULIA OLEFINATION; PARALLEL; Stereoisomer; Sex pheromone; Sulfone; Olefination; Insecta; HPLC chromatography; Natural product; Alcohol; NMR spectrometry; Pinus; Diprionidae; Total synthesis; Chemical reduction; Ester; Arthropoda; Gymnospermae; Organic fluorine compounds; Tagging; Coniferales; Spermatophyta; Hymenoptera; Invertebrata; Chemical synthesis; Mass spectrometry
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo051526a

The application of fluorous mixture synthesis (FMS) for accessing natural products and their stereoisomers was validated by the total synthesis of all 16 stereoisomers of the pine sawfly sex pheromone. Four fluorous p-methoxybenzyl groups were used as tags, and a “4-mix-4-split” approach was employed in a divergent synthesis. This paper presents the details of the FMS of pine sawfly sex pheromones with an emphasis on identification and solving of problems encountered when working with fluorous mixtures.