“…Most commonly,t hey are converted into b-hydroxy nitriles using either TMSCl/NaI [13a] or NaSEt [13b] or reduced to bhydroxy amines.A fter extensive experimentation, including transition-metal-catalyzed couplings,radical dehalogenations, or substitution reactions with vinyl anions,n oe ffective functionalization of 19 could be established. Additionally, when 19 was converted into the corresponding b-hydroxy nitrile using TMSCl/NaI, reduction to the aldehyde was found to be exceedingly difficult under av ariety of conditions (iBu 2 AlH, iBu 2 AlH·SMe 2 , [14a] Red-Al, Li(iBu) 2 (nBu)AlH, [14b] Ra-Ni/NaH 2 PO 2 [14c] or Ra-Ni/formic acid [14d] )a nd alternative approaches were deemed necessary.T hus,b romide-methoxide exchange, [15] followed by Ra-Ni-mediated hydrogenolysis of the NÀOb ond smoothly provided ester 21 in 91 % overall yield (Scheme 3). While ester reduction with iBu 2 AlH led to decomposition of both starting material and product, the use of non-Lewis-acidic Li(iBu) 2 (nBu)AlH (generated from iBu 2 AlH and nBuLi) [16] cleanly provided the corresponding diol in 89 %yield.…”