Spatol synthesis

During studies directed towards the synthesis of spatol, Salomon and Murthi studied epoxysilane 153 bearing a temporary tether (Scheme 5.36), which circumvented the potential problem of configurational instability described above [57]. 

A formal total synthesis of racemic spatol was accomplished by M. Harmata et al. using an intermolecular [4+3] cycloaddition of a haiogenated cyclopentenyl cation with cyclopentadiene followed by a quasi-Favorskii rearrangement as the key steps. ... 

Harmata, M., Rashatasakhon, P. A 4 + 3 Cycloaddition Approach to the Synthesis of Spatol. A Formal Total Synthesis of Racemic Spatol. Org. Lett. 2001, 3, 2533-2535. 

Intermolecular [2+2] photocycloaddition has been applied to the synthesis of a wide variety of natural products and their analogs, which frequently contain four-membered rings in highly ordered chiral environments, or a structure which can be readily derived from the [2+2] cycloadduct. The marine natural product Spatol (57) contains a three fused ring system (see Scheme 16). This has been... 

Scheme 7.40 Formal synthesis of spatol via a r4+3Vcycloaddition/quasi-Favorskii rearrangement sequence.

As part of our program exploring the (4+3)-cycloaddition/quasi-Favorskii reaction sequence, we undertook a formal total synthesis of spatol fFigure 7.9T an interesting natural product possessing a unique diepoxide, a 5-4-5 ring-fused carbocyclic core, and antitumor... 

Tanaka, M., Tomioka, K., and Koga, K. (1985) The first total synthesis of (+)-spatol with natural configuration. Tetrahedron Lett., 26, 6109-6112. 

Salomon, R.G., Basu, B., Roy, S., and Sharma, R.B. (1989) Total synthesis of (+)-spatol a stereospedfic construction of vicinal diepoxides from 2,3-epoxy-l,4-diols. Tetrahedron Lett., 30, 4621-4624. 

Dauben, W.G. and Kowalczyk, B.A. (1990) Total synthesis of (13Z)-spata-13(15),17-diene, and the formal synthesis of spatol. Tetrahedron Lett., 31, 635-638. 

Harmata, M. and Rashatasakhon, P. (2001) A 4+3 cydoaddition approach to the synthesis of spatol a formal total synthesis of racemic spatol. Org. Lett., 3, 2533-2535. 

The high facial stereoselectivity observed for the [2-t-2]-photocycloadditions of alkenes with chiral butenolides and the polyfimctional nature of the cycloadducts have led to interesting new apphcations in the field of natural products. The total synthesis of (-t-)-stoechospermoP and (-l-)-spatol (Scheme 23), as well as new syntheses of (-i-)-grandisol, > including photochemical cycloaddition as a key step, have been recently reported (Scheme 23). 

---