Limitations of t-butyldimethylsilyl as a protecting group for hydroxy-functions

Dodd, George H.; Golding, Bernard T.; Ioannou, Panayiotis V.

doi:10.1039/c39750000249

Cited by 41 publications

(31 citation statements)

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“…Digestion of dimer 8 with VPD should give exclusively uridine-5'-phosphate and 5'-amino-deoxy-uridine (13). In this case too the digestion products were identical, in every aspect, with uridine-5'-phosphate and synthetically-prepared 5'-amino-deoxy-uridine (13). The above findings clearly indicate that the compound in peak (ii) of Fig.…”

Section: Resultssupporting

confidence: 59%

“…The identity of the latter compound was independently confirmed by comparison with synthetically-prepared 14 (Scheme 3). Digestion of dimer 8 with VPD should give exclusively uridine-5'-phosphate and 5'-amino-deoxy-uridine (13). In this case too the digestion products were identical, in every aspect, with uridine-5'-phosphate and synthetically-prepared 5'-amino-deoxy-uridine (13).…”

Section: Resultsmentioning

confidence: 95%

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Neighbouring group participation in the unblocking of phosphotriesters of nucleic acids

et al. 1979

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Two examples of neighbouring group participation during the removal of protecting groups from phosphotriesters of partially or fully protected intermediates of nucleic acids are presented. The first example shows that ammonolysis of aryl groups from phosphotriesters of partially protected -5'-hydroxy free -nucleic acids (e.g., 4b; Ar=2ClC H4) gives rise to the formation of unnatural nucleic acids (e.g., 7 and t). The second one illustrates that fluoride ion promoted hydrolysis of 2,2,2-trichloroethyl groups from phosphotriesters of fully protected nucleic acids (e.g., 18a), having t-butyldimethylsilyl groups at the 2'-positions, leads to the formation of a considerable amount of side-products (e.g., 20 and 21).

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Section: Resultssupporting

confidence: 59%

Section: Resultsmentioning

confidence: 95%

Neighbouring group participation in the unblocking of phosphotriesters of nucleic acids

et al. 1979

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“…This observation has been recently recorded by others also (5). such, complements the tetrahydropyranyl and benzyl groups in a variety of synthetic transformations.…”

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confidence: 78%

The Preparation and Synthetic Utility of tert-Butyldiphenylsilyl Ethers

Hanessian¹,

Lavallée²

1975

Can. J. Chem.

471

189

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The utility of tert-butyldiphenylsilyl chloride as a reagent for the protection of hydroxyl groups was explored. The corresponding tert-BDPSi ethers have much greater stability to acids, and under conditions of hydrogenolysis, than related silyl and trityl ethers. Preferential removal of trityl, tetrahydropyranyl, benzyl, and other silyl ethers and acetals can be effected in presence of tert-EDPSi ethers. Treatment with fluoride ion causes smooth cleavage of the latter.

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“…[15] One should mention that regioselectivity of the opening of an epoxide ring can be significantly increased if an additional functionality permitting coordination of metal cation [24] or boranes [25] is present. An alternative two-step tactic involving insertion of organosilicon halides into epoxides [26] with a subsequent deprotection of the thus obtained O-silylated precursors of vicinal halohydrins [24] is incapable to circumvent the aforementioned shortcomings, as (i) halosilylating fission of oxiranes is not always completely regioselective and varies widely depending upon steric factors in the substrates [24,26] and (ii) the removal of relatively labile trimethylsilyl (TMS) and tert-butyldimethylsilyl (TBDMS) ethers requires conditions that either preclude access to derivatives with acid-, [24] base-, [27] or oxidation/reduction-sensitive functionalities, [28] or they are known to trigger prohibitive structural rearrangements of the molecular skeleton (e.g., acyl migration, racemization, etc.) after exposure of a free hydroxy group adjacent to an acyl substituent.…”

Section: Introductionmentioning

confidence: 99%

Regioselective and Stereospecific Halosilylating Cleavage of the Oxirane System of Glycidol Derivatives as an Efficient Strategy to C2‐O‐Functionalized C3‐Vicinal Halohydrins

Stamatov

Stawiński

2008

Eur J Org Chem

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Glycidyl esters and ethers undergo a regioselective and stereospecific opening of the oxirane ring upon treatment with trimethylsilyl halides (TMSX, X = Cl, Br, or I) in the presence of pyridine to produce the corresponding C2-O-trimethylsilyl-3(1)-halo-sn-glycerols in high yields. Trifluoroacetylation across the trimethylsilyloxy system of such C3-synthons with trifluoroacetic anhydride (TFAA) in the presence of a halide anion (e.g. Bu 4 NX; X = Cl, Br, or I), followed by removal of the trifluoroacetyl transient protection, pro-

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Limitations of t-butyldimethylsilyl as a protecting group for hydroxy-functions

Cited by 41 publications

References 0 publications

Neighbouring group participation in the unblocking of phosphotriesters of nucleic acids

Neighbouring group participation in the unblocking of phosphotriesters of nucleic acids

The Preparation and Synthetic Utility of tert-Butyldiphenylsilyl Ethers

Regioselective and Stereospecific Halosilylating Cleavage of the Oxirane System of Glycidol Derivatives as an Efficient Strategy to C2‐O‐Functionalized C3‐Vicinal Halohydrins

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