Protecting groups

Jarowicki, Krzysztof; Kocieński, Philip

doi:10.1039/a803688h

Cited by 35 publications

(20 citation statements)

References 179 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The DMTr protecting group was incorporated and the conversion of the secondary alcohol 10 to phosphoramidite 11 was performed. The base-labile cyanoethyl group [51–52] is known to be resistant under synthesis conditions for the preparation of the phosphoramidite building block and for solid-phase oligonucleotide synthesis [49,53]. …”

Section: Resultsmentioning

confidence: 99%

DNA functionalization by dynamic chemistry

Kanlidere¹,

Jochim²,

Cal³

et al. 2016

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

SummaryDynamic combinatorial chemistry (DCC) is an attractive method to efficiently generate libraries of molecules from simpler building blocks by reversible reactions under thermodynamic control. Here we focus on the chemical modification of DNA oligonucleotides with acyclic diol linkers and demonstrate their potential for the deoxyribonucleic acid functionalization and generation of libraries of reversibly interconverting building blocks. The syntheses of phosphoramidite building blocks derived from D-threoninol are presented in two variants with protected amino or thiol groups. The threoninol building blocks were successfully incorporated via automated solid-phase synthesis into 13mer oligonucleotides. The amino group containing phosphoramidite was used together with complementary single-strand DNA templates that influenced the Watson–Crick base-pairing equilibrium in the mixture with a set of aldehyde modified nucleobases. A significant fraction of all possible base-pair mismatches was obtained, whereas, the highest selectivity (over 80%) was found for the guanine aldehyde templated by the complementary cytosine containing DNA. The elevated occurrence of mismatches can be explained by increased backbone plasticity derived from the linear threoninol building block as a cyclic deoxyribose analogue.

show abstract

Section: Resultsmentioning

confidence: 99%

DNA functionalization by dynamic chemistry

Kanlidere¹,

Jochim²,

Cal³

et al. 2016

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…3 The success of benzyl ethers as protective synthetic intermediates of alcoholic groups mainly lies in their aptitude to release the benzyl moiety under the action of different reagents, which can be chosen depending on the sensitivity of the molecule to reaction conditions. 4 The presence of suitable functional groups on the phenyl ring of benzylic reagents can modulate their protecting/deprotecting features toward different OH groups and, therefore, enhance their applicability as orthogonal protecting groups for polyhydroxy compounds. 5 However, it would be highly desirable to obtain benzyl ethers (BnOR) from alcoholic substrates (ROH) by using the corresponding benzyl alcohols (BnOH), which are the most convenient sources of benzyl groups.…”

Section: Introductionmentioning

confidence: 99%

Does a chiral alcohol really racemize when its OH group is protected with Boyer's reaction?

2009

View full text Add to dashboard Cite

Chiral reactants have been employed for assessing the real stereochemistry of the BiBr3-catalyzed synthesis of benzylic ethers, a very useful reaction for protecting alcoholic groups. The results of this investigation are in clear contrast with the conclusions of previous studies (Boyer et al., Tetrahedron 2001;57:1917-1921). Indeed, chiral GC-MS analysis of the ethereal products gives unequivocal evidence of the complete racemization of the benzylic moiety and the complete retention of configuration of the protected alcoholic substrate. Such findings make BiBr3 a powerful and stereochemically preservative catalyst for benzylation of chiral alcohols, and a potential candidate for orthogonal protecting group strategies applicable to polyhydroxy compounds.

show abstract

“…For the formation of silyl ethers of tert-alcohols with more bulky silyl PGs such as triethylsilyl (TES) [36] and tertbutyldimethylsilyl (TBS) [28] ethers, which are synthetically more useful than TMS ethers due to their improved stability towards acids and bases, [37][38][39] silyl triflate and silyl perchlorate reagents are generally relied upon [e.g. TBS-OTf (1.5 eq.…”

Section: Entrymentioning

confidence: 99%

Amines vs. N‐Oxides as Organocatalysts for Acylation, Sulfonylation and Silylation of Alcohols: 1‐Methylimidazole N‐Oxide as an Efficient Catalyst for Silylation of Tertiary Alcohols

Murray

Spivey

2015

Adv Synth Catal

View full text Add to dashboard Cite

A comparison of the relative catalytic efficiencies of Lewisbasic amines vs. N-oxides for the acylation, sulfonylation and silylation of primary, secondary and tertiary alcohols is reported. Whilst the amines are generally superior to the N-oxides for acylation, the N-oxides are superior for sulfonylation and silylation. In particular, 1-methyl-imidazole-N-oxide (NMI-O) is found to be a highly efficient catalyst for sulfonylation and silylation reactions. To the best of our knowledge, NMI-O is the first amine or N-oxide Lewis basic organocatalyst capable of promoting the efficient silylation of tertalcohols in high yield with low catalyst loading under mild reaction conditions.

show abstract

Protecting groups

Cited by 35 publications

References 179 publications

DNA functionalization by dynamic chemistry

DNA functionalization by dynamic chemistry

Does a chiral alcohol really racemize when its OH group is protected with Boyer's reaction?

Amines vs. N‐Oxides as Organocatalysts for Acylation, Sulfonylation and Silylation of Alcohols: 1‐Methylimidazole N‐Oxide as an Efficient Catalyst for Silylation of Tertiary Alcohols

Contact Info

Product

Resources

About