Selective Hydrovinylation/Hydroacylation KOt-Bu DMSOMH o 62%, steps 62%, 2 steps KF, H2O2 nCeR E:z=1:9 50%.2 steps Tamao, K; Maeda, K. Yamaguchi, T. Ito, Y.J. Am. Chem. Soc. 1989, 111, 4984 Dig-Cyclizations AIBN 65%, 2 step 1)Ph3 SnH, AIBN Joumet, M. Malacria, M. J. Org. Chem. 1992, 57, 3085 33A-103/11966:00PMMe Me O Me Si Br Me Me Me O Si Me Me Me Me Me OH Me Me Me OH Me Me TMS Me OH Me Me O Me OH Me Me Br Me Me O Me Si Br Me Me Me O Si Me Me Me Me n-C6H13 n-C6H13 Me OH Me Me O n-C6H13 Me OH Me Me n-C6H13 O R Si Me Me H H H O Si Me Me H H H R n-Bu3SnH AIBN MeLi 52%, 2 steps KF, H2O2 KOt-Bu, DMSO/H2O 62%, 2steps 30%, 2 steps 62%, 2 steps NBS, DMF Selective Hydrovinylation/Hydroacylation: KOt-Bu DMSO/H2O 33%, 2 steps KF, H2O2 50%, 2 steps n-Bu3SnH AIBN Tamao, K.; Maeda, K.; Yamaguchi, T.; Ito, Y. J. Am. Chem. Soc. 1989, 111, 4984. . E:Z = 1:9 E Only . 1 isomer Dig-Cyclizations: O Me Me Si Br Me Me Si O Me Me Me Me HO Me Me HO O Me Si Br Me Me Si O Me Me Me HO Me HO O Me Me Si Br Me Me Si O Me Me Me Me HO Me Me TMS OTHP OTHP OTHP C4H9 C4H9 C4H9 O Ph Me Me Si Br Me Me HO HO Ph O TMS Me Me E:Z = 95:5 Ph3SnH AIBN Ph3SnH AIBN Si Br Me Me Ph3SnH AIBN MeLi 60%, 2 steps KF, H2O2 65%, 2 steps E Only KF, H2O2 70%, 2 steps 1) Ph3SnH, AIBN 2) KF, H2O2 85%, 2 steps HO HO TMS E:Z = 25:75 E Only 1) Ph3SnH, AIBN 2) KF, H2O2 84%, 2 steps E:Z = 35:65 Journet, M.; Malacria, M. J. Org. Chem. 1992, 57, 3085. 33A-10 3/11/96 6:00 PM