Silanediol versus chlorosilanol: hydrolyses and hydrogen-bonding catalyses with fenchole-based silanes

Biphenyl-2,2'-bisfenchyloxydichlorosilane (7, BIFOXSiCl₂) is synthesized and employed as precursor for the new silanols biphenyl-2,2'-bisfenchyloxychlorosilanol (8, BIFOXSiCl(OH)) and biphenyl-2,2'-bisfenchyloxysilanediol (9, BIFOXSi(OH)₂). BIFOXSiCl₂ (7) shows a remarkable stability against hydrolysis, yielding silanediol 9 under enforced conditions. A kinetic study for the hydrolysis of dichlorosilane 7 shows a 263 times slower reaction compared to reference bis-(2,4,6-tri-tert-butylphenoxy)dichlorosilane (14), known for its low hydrolytic reactivity. Computational analyses explain the slow hydrolyses of BIFOXSiCl₂ (7) to BIFOXSiCl(OH) (8, E _a = 32.6 kcal mol^-1) and BIFOXSiCl(OH) (8) to BIFOXSi(OH)₂ (9, E _a = 31.4 kcal mol^-1) with high activation barriers, enforced by endo fenchone units. Crystal structure analyses of silanediol 9 with acetone show shorter hydrogen bonds between the Si-OH groups and the oxygen of the bound acetone (OH···O 1.88(3)-2.05(2) Å) than with chlorosilanol 8 (OH···2.16(0) Å). Due to its two hydroxy units, the silanediol 9 shows higher catalytic activity as hydrogen bond donor than chlorosilanol 8, e.g., C-C coupling N-acyl Mannich reaction of silyl ketene acetals 11 with N-acylisoquinolinium ions (up to 85% yield and 12% ee), reaction of 1-chloroisochroman (18) and silyl ketene acetals 11 (up to 85% yield and 5% ee), reaction of chromen-4-one (20) and silyl ketene acetals 11 (up to 98% yield and 4% ee).