Scheme 3. Synthesis of d4-1 and d7-1. (a) (tBu)2PHBH3, 40% NaOD(D2O), TBAB, toluene, rt, 16 h (98%, 95%D), (b) (i) HBF4·OEt2, MeOD, 80 °C, 16 h (ii) DIPA polymer bound, MeOD, rt, 1 h (iii) [Ir(COD)2]BF4 (47%), (c) CO(g) (5 Bar), NaCO3, Pd(OAc)2, DPPB, EtOH, 100 °C, 16 h (55%), (d) 5% Pd/C, D2(g), Et3N, D2O/THF, rt, 5 h (82%, 98% D), (e) NaBD4, MeOD, 65 °C, 2 h (86%, 98% D), (f) SOCl2, THF, 65 °C, 1 h (93%), (g) (tBu)2PHBH3, 40% NaOD(D2O), TBAB, toluene, rt, 16 h (99%), (h) (i) HBF4·OEt2, MeOD, 80 °C, 16 h (ii) DIPA-polymer bound, MeOD, rt, 1 h (iii) [Ir(COD)2]BF4 (57%).
