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Finalization of the total synthesis of floyocidin B (4) and 27: (a) n‐BuLi (1.0 eq.), THF, −100 °C, 20 min; 5 min without cooling; 26 % for 7, 81 % for 25; (b) APhos Pd G3 (0.1 eq.), Cs2CO3, trans‐1‐penten‐1‐ylboronic acid pinacol ester, 1,4‐dioxane/H2O 8 : 1, 100 °C; 51 % for 24, 84 % for 26; (c) TBAF, HOAc, THF; 60 % for 4, 93 % ee; 65 % for 27, 93 % ee; (d) PPh3, HOAc, DIAD, THF; 84 %; (e) LiOH, THF/H2O 5 : 1; 51 %.
