Hydroxyl Protecting Groups 2 Silyl Ethers

Poly (vinyl alcohol) macromonomers having the hydroxyl groups protected as silyl ethers were prepared using p-formylstyrene as initiator [218] (Scheme 67). 

Coordination polymerization of hydroxyl, carboxyl and amino monomers can also be effected by the judicious use of protecting groups. For example, amino and hydroxyl monomers have been protected by silyl ethers and aluminate salts for Ziegler Natta and/or metallocene polynrierization and carboxyl monomers have been protected via aluminate salts. Alternatively, organoborane synthons have been used to carry... 

Silyl ethers have an important role as hydroxyl-protecting groups/ Alcohols can be easily converted to trimethylsilyl ethers by reaction with trimethylsilyl chloride in the presence of an amine or by heating with hexamethyldisilazane. Although these are useful compounds when the objective is preparation of a less polar derivative of... 

OH must help subsequent isomerization, because ( )-30 is stable in the presence of 1, even after 2 d at 70°C. To test whether the bulk of the silyl ether protecting group was responsible for this reactivity difference, compound 32 was allowed to isomerize, forming a high yield of (ii)-33 at room temperature. In this case, heating at 70°C for 15 h does seem to lead to traces of what is tentatively identified as 34, but the second isomerization is clearly much slower than the first. Further studies are planned to elucidate the role of a hydroxyl substituent in alkene isomerization... 

The hydroxyl group was usually protected, because cyanohydrins have tendency to racemization or even decomposition. Vinyl ethers or acetal and acid catalysts furnish acetals [62]. Trialkylsilyl chlorides and imidazole are used to give silyl ethers [63]. Commonly used protective groups are silyl ether, ester, methoxy isopropyl (MIP) ether, and tetrahydro-pyranyl ether. ( -Protected cyanohydrins are tolerant to a wider range of cyanide/nitrile transformations and are utilized widely in the synthesis of compounds of synthetic relevance in organic chemistry. 

A hydroxyl group can also be protected by converting it to a silyl ether group. 

The secondary hydroxyl group of 206 is now protected with a PMB group. Reduction of the resulting diastereomeric mixture 207 gives the corresponding alcohol 208, which is then separated to give a single stereoisomer. A silyl ether... 

Reductive elimination of an allylic diol group. A new synthesis of vitamin A involves reduction of the allylic diol 1, prepared in several steps from JJ-ionone, with a low valent titanium formed from TiCl3 and LiAlH, in the ratio 2 1. Thus, the allylic diol group of 1 [either (E) or (Z)] is reduced to an (E,E)-1,3-diene group to form the silyl ether (2) of vitamin A.1 When the primary hydroxyl group is protected as an acetate, the reduction gives a mixture of (E)- and (Z)-2. 

The alcoholysis of hydrosilanes (or the 0-silylation of alcohols) represents a crucial way of synthesizing the silyl ethers that are among the most widely used protective groups of the hydroxyl functionality in organic synthesis (Equation 14.14) [73]. 

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