Total Synthesis of -Dactylolide

Ring-closing metathesis can also be used to close larger rings. In the course of a total synthesis of (-)-dactylolide, Michael P. Jennings of the Unversity of Alabama described (Organic Lett. 2005, 7,... 

One key element of the total synthesis of (-)-dactylolide (-)- developed by McLeod et al. is a [3,3]-sigmatropic Ireland-Claisen rearrangement which allows the selective formation of the stereogenic centre at C-19. 

Scheme 18.66 Seleno Mislow-Evans applied for allylic transposition in total synthesis of (+)-dactylolide/ ...

Hoye achieved the total synthesis of (-)-dactylolide via two distinct macro-cyclization strategies, involving Ti(IV)-mediated macrolactonization of an epoxy-acid (route A) and a RCM macrocyclization (route B) (Scheme 29). The czs-2,6-disubstituted-4-methylene tetrahydropyran was constructed by Prins... 

Floreancig and coworkers employed a sequential Peterson olefmation and Prins cyclisation reaction in their total synthesis of (+)-dactylolide hence neatly illustrating the versatility of the Peterson reaction. The P hydroxysilane 103 was synthesised in situ by the double addition of the necessary Grignard reagent onto ester 102. Treatment of the resulting tertiary alcohol with pyridinium triflate and magnesium sulfate then prompted the Peterson olefmation and subsequent Prins cyclisation to occur, affording tetrahydropyran 106 in 75% yield. 

Lee, Kiyoun Kim, Hyoungsu Hong, Jiyong. N-Heterocyclic Carbene Catalyzed Oxidative Macrolactonization Total Synthesis of (+)-Dactylolide Angew. Chem. Int. Ed., 2012, 51, 5735-5738. 

Scheme 2.60 McLeod s total synthesis of (-)-dactylolide Uenishi s Synthesis [167]...

Ding, F. and Jennings, M.P. (2008) Total synthesis of (-)-dactylolide and formal synthesis of (—)-zampanolide via target oriented P-C-glycoside formation. J. Org. Chem., 73, 5965-5976. 

---