Synthetic study on biologically active polyols using mobility of (diene)Fe(CO)_3 complexes.

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1. We have found a convenient method for the transformation of (polyene)Fe(CO)_3 complexes bearing an electron-withdrawing group (aldehyde, ketone, ester, and nitrile) into desired migrated products by treatment with the base such as KN(TMS)_2, LiCH_2CN, and NaH.2. When the Fe(CO)_3 group moves on the polyene side-chain via the 1, 3- or 1, 5-migration, the chirality of (diene)Fe(CO)_3 group was preserved and the reaction proceeds with inversion or retention of configuration, respectively.3. We have succeeded in the diastereoselective dihydroxylation of the umcomplexed olefin with OsO_4 by using chirality of the Fe(CO)_3 group. In addition, regio- and stereoselective introduction of various nucleophiles into the above diol complexes could be carried out under Lewis-acidic conditions via the corresponding orthoester.4. By successive treatment of triene and tetraene Fe(CO)_3 complexes with base-mediated 1, n-maigration and the stereoselective reduction of the ketones, chiral 1, 8- and 1, 10-diols, which could not prepared by the standard procedure, were synthesised stereoselectively.5. With an aim of the asymmetric synthesis of didemnaketal A and macrolactin A, which are known as HIV-1 protease inhibitors, we examined the iterative use of the stereospecific 1, n-migration reaction. Consequently, we have established the asymmetric synthesis of several type of polyols such as 1, 2-syn-2, 3-anti-3, 4-syn-tetraol derivative and 1, 3-anti-diol derivatives.