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Synthesis of building block 21: a) Ru{(S)‐Tol‐BINAP}(OAc)2, H2 (50 bar), MeOH, rt, 16 h, 94 %; b) Imidazole, TBDPSCl, CH2Cl2, 0 °C, 4 h, 95 %; c) NBS, 2:1 THF/H2O, 0 °C, 5 h; d) KOt‐Bu, THF, 0 °C, 30 min, 49 % over 2‐steps; e) H5IO6, THF, 0 °C, 1 h; f) (carbethoxyethylidene)triphenylphosphorane, THF, reflux, 16 h, 72 % over 2‐steps; g) DIBAL‐H, CH2Cl2, −78 °C, 30 min, 98 %; h) 1 mol % Cat I, H2 (50 bar), CH2Cl2, 0 °C, 16 h, 94 %.
