The Oxidation of Primary Trimethylsilyl Ethers to Aldehydes – a selective conversion of a primary hydroxy group into an aldehyde group in the presence of a secondary hydroxy group

Mahrwald, Rainer; Theil, Fritz; Schick, H.; Schwarz, S.; Palme, Hans-Joachim; Weber, Gisela

doi:10.1002/prac.19863280517

Cited by 29 publications

(13 citation statements)

References 20 publications

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“…The α,β‐unsaturated methyl ester 1f and its free carboxylic acid 1g were synthesized as depicted in Scheme 3, as described previously [38] and the modifications which were recently introduced for the preparation of C‐6 aldehyde derivatives of Glc [15]. The key step is the use of Collins reagent for the selective oxidation of the primary trimethylsilyl ether of the fully silylated monosaccharide 8 to an aldehyde (step ii).…”

Section: Synthesis Of Inhibitorsmentioning

confidence: 99%

The glucose‐specific carrier of the Escherichia coli phosphotransferase system

Garcia-Alles

Navdaeva

Haenni

et al. 2002

European Journal of Biochemistry

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Thirteen glucose analogues bearing electrophilic groups were synthesized (five of them for the first time) and screened as inhibitors of the glucose transporter (EII Glc ) of the Escherichia coli phosphoenolpyruvate-sugar phosphotransferase system (PTS). 2¢,3¢-Epoxypropyl b-D-glucopyranoside (3a) is an inhibitor and also a pseudosubstrate. Five analogues are inhibitors of nonvectorial Glc phosphorylation by EII Glc but not pseudosubstrates. They are selective for EII Glc as demonstrated by comparison with EII Man, another Glc-specific but structurally different transporter. 3a is the only analogue that inhibits EII Glc by binding to the highaffinity cytoplasmic binding site and also strongly inhibits sugar uptake mediated by this transporter. The most potent inhibitor in vitro, methyl 6,7-anhydro-D,L-glycero-a-Dgluco-heptopyranoside (1d), preferentially interacts with the low-affinity cytoplasmic site but only weakly inhibits Glc uptake. Binding and/or phosphorylation from the cytoplasmic side of EII Glc is more permissive than sugar binding and/or translocation of substrates via the periplasmic site. EII Glc is rapidly inactivated by the 6-O-bromoacetyl esters of methyl a-D-glucopyranoside (1a) and methyl a-D-manno- ) of diverse specificity and structure are components of the bacterial phosphoenolpyruvate-sugar phosphotransferase system (PTS) [4]. The PTS in addition comprises a number of proteins that act as allosteric regulators of enzymes and/ or transcription factors.The PTS transporters are homodimers, as indicated by cross-linking, ultracentrifugation, gel filtration, interallelic complementation and cryo-electron crystallography [5][6][7][8][9]. One protomer comprises three (or four) functional units, IIA, IIB and IIC(IID), which occur either as protein subunits or as domains in polypeptide chains. IIA and IIB sequentially transfer phosphoryl groups from HPr to the transported sugars. IIC contains the major determinants for sugar recognition and translocation, as inferred from binding studies [10] and the substrate selectivity of a chimeric EII GlcNAc/Glc [11]. EI, HPr and IIA are phosphorylated at His, whereas IIB domains are phosphorylated at Cys421 in EII Glc and at His175 in EII Man. EII Glc is specific for Glc, but EII Man has a broader substrate specificity for Glc, Man, and other derivatives of Glc altered at the C-2 carbon. Both transporters phosphorylate their hexose substrates at OH-6. In spite of their overlapping substrate specificity and analogous mechanism of action, EII Glc and EII Man do not share amino-acid sequence similarity, and, as judged by the known X-ray structures of their cytoplasmic domains, also assume completely different folds (for a review see [12]). The topology of the membrane-spanning units IIC Glc and IIC Man -IID Man are also different, as judged by the characterization of protein fusions between C-terminally truncated IIC(D) domains with alkaline phosphatase and b-galactosidase [13,14]. Whereas the sites of EII phosphorylation are known and easily recognized from the ...

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Section: Synthesis Of Inhibitorsmentioning

confidence: 99%

The glucose‐specific carrier of the Escherichia coli phosphotransferase system

Garcia-Alles

Navdaeva

Haenni

et al. 2002

European Journal of Biochemistry

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“…previously, selective oxidative deprotection of the primary alcohol TMS ether with Collins oxidation, [21][22][23] Takai olefination 24,25 using CH 3 CHI 2 in the presence of CrCl 2 , and removal of the remaining TMS ether, afforded the analogue, ent-4-deoxy-2,3-di-epi-dinemasone BC (3), in 47% yield over three steps as the only product (E/Z > 95:05), the configuration of 3 was also determined by NOESY experiment (Scheme 3).…”

Section: Baeyer-villiger Oxidationmentioning

confidence: 99%

Concise and direct construction of cis-pyrano[4,3-b]pyran-5-one skeleton from glucal derivatives: synthesis of ent-4-deoxy-2,3-di-epi-dinemasone BC

Xue

Yin

et al. 2015

Tetrahedron Letters

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“…Compound (1) was obtained from methyl ␣-Dglucopyranoside according to a previously described procedure [15]; D-glucopyranosiduronic acid (2) is commercially available. Compounds (3) and (4) were obtained by selective oxidation of the C6 hydroxylic group of methyl ␣-D-glucopyranoside and C6 and C6' hydroxylic groups of 1-methyl D-(+)-cellobiose, respectively, via the TEMPO/NaClO method to give the corresponding sodium carboxylates [16].…”

Section: Synthesesmentioning

confidence: 99%