Trehazolin synthesis activities

B. E. Ledford and E. M. Carreira, Total synthesis of (+)-trehazolin Optically active spirocyclohep-tadienes as useful precursors for the synthesis of aminocyclopentitols, J. Am. Chem. Soc., 117 (1995) 11811-11812. 

Also, Ogawa s group reported the s)mthesis of racemic trehazolin aminocyclitol derivatives, as well as trehazolin and its diastereoisomers from wtyo-inositol, and thus contributed independently to the determination of the correct stereochemistry of trehazolin [182,183,184,185,186]. The successful total synthesis of trehazolin (223) encouraged Kobayashi and Shiozaki et al. to investigate stmcture-activity relationships regarding the inhibitory activities towards vari-... 

On the other hand, Carreira et al. also reported the total synthesis of trehazolin from the optically active spirocycloheptadiene [196], which was prepared from the (7 )-epichlorohydrin 282 and lithium cyclopentadienide, shown in O Scheme 41. Treatment of lithium cyclopentadi-enide (CpH+BuLi) with (/J)-epichlorohydrin 282 afforded the optically active spirocycloheptadiene 283 in 91% ee. Compound 283 was converted into trichloroacetimidate 284 by treatment of NaH and CI3CCN [197], and subsequent treatment of 284 with I(. -cohidine)2C104 gave the alcohol 287 via the unstable intermediates 285 and 286. After silylation of the secondary hydroxy group of 287, the imidate underwent nucleophilic opening upon treatment of the corresponding silyl-protected imidate with Li2NiBr4 to yield the cyclopropylcarbinyl bro-... 

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