An efficient multigram-scale synthesis of 4-(ω-chloroalkoxy)phenols

Zinin, Alexander I.; Stepanova, Elena V.; Jost, U.; Kondakov, N. N.; Shpirt, Anna M.; Chizhov, Alexander O.; Торгов, В. И.; Kononov, L. O.

doi:10.1007/s11172-017-1732-9

Cited by 16 publications

(6 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…HCl in AcOEt). Unexpectedly, the only isolable product was acetate of phenol 2 a (CPP‐OAc) [10] without traces of any sialoside (see Supporting information for the details).…”

Section: Resultsmentioning

confidence: 99%

“…General methods : The reactions were performed with the use of commercial reagents (Aldrich, Fluka, Acros Organics). Sialyl chlorides 1 a [35b] and 1 b , [32] 4‐(3‐chloropropoxy)phenol ( 2 a ) [10] and 4‐(2‐chloroethoxy)phenol ( 2 b ) [10] were synthesized according to previously reported procedures. Sialyl chloride 1 a contained 12.3 % of the corresponding glycal [35] as an impurity ( 1 H NMR data).…”

Section: Methodsmentioning

confidence: 99%

“…However, the preparation of Janus glycosides of N ‐acetylneuraminic acid (sialosides) remained an unsolved task. Since sialoconjugates are of great importance in glycobiology, [4c,9] we decided to fill this gap and prepare CPP sialoside 3 a (Scheme 1) by glycosylation of 4‐(3‐chloropropoxy)phenol [10] (CPP−OH, 2 a ).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Black Swan in Phase Transfer Catalysis: Influence of Mixing Mode on the Stereoselectivity of Glycosylation

et al. 2022

View full text Add to dashboard Cite

Phase transfer catalysis (PTC) is widely used for the preparation of anomerically pure aryl glycosides by glycosylation of phenols with glycosyl halides. Here, we attempted to synthesize 4‐(3‐chloropropoxy)phenyl (CPP) sialoside – a useful Janus glycoside for neoglycoconjugate synthesis. A batch glycosylation reaction under typical PTC conditions (N‐acetylsialyl chloride, 4‐(3‐chloropropoxy)phenol, Bu4NHSO4, AcOEt, 10 % aq Na2CO3) resulted in formation of CPP sialoside as a single anomer, albeit in low yield. Conversely, the PTC glycosylation in flow using Comet X‐01 micromixer doubled the yield of CPP sialoside, which was obtained as a mixture of anomers suggesting the change in the reaction mechanism apparently induced by the change in mixing mode. An increase in flow rate led to further loss of stereoselectivity while the use of T‐shaped mixer increased stereoselectivity. Similar results were obtained for N,N‐diacetylsialyl chloride and two other para‐alkoxy‐substituted phenols suggesting generality of the discovered phenomenon.

show abstract

“…HCl in AcOEt). Unexpectedly, the only isolable product was acetate of phenol 2 a (CPP‐OAc) [10] without traces of any sialoside (see Supporting information for the details).…”

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Black Swan in Phase Transfer Catalysis: Influence of Mixing Mode on the Stereoselectivity of Glycosylation

et al. 2022

View full text Add to dashboard Cite

show abstract

“…These opportunities can be further used for the preparation of a wide range of neoglycoconjugates. 33 The β-anomer of lactose octaacetate 18 34 was glycosidated with 4-(3-chloropropoxy)phenol 35 (CPP-OH) in the presence of BF 3 •OEt 2 /Et 3 N 36 to afford glycoside 19. Lactosyl acceptor 24 with an unprotected hydroxy group at C-4′ was obtained from 19 using the following standard steps essentially as described previously 37 (Scheme 4): removal of the O-acetyl groups (19→20), installation of 4′,6′-O-benzylidene protection (20→21) with subsequent O-benzoylation (21→22), removal of the 4′,6′-O-benzylidene group under acidic conditions (22→23) and selective O-benzoylation (23→24).…”

Section: Figure 2 Galactosyl Acceptors 9-12mentioning

confidence: 99%

A Novel Glycosyl Donor with a Triisopropylsilyl Nonparticipating Group in Benzyl-Free Stereoselective 1,2-cis-Galactosylation

Abronina

Zinin

Malysheva

et al. 2017

Synlett

View full text Add to dashboard Cite

A novel glycosyl donor with a triisopropylsilyl (TIPS) nonparticipating group at O-2 is introduced for use in 1,2-cis-galactosylation. Coupling the 2-O-TIPS-substituted thiogalactoside donor with a series of mono- and disaccharide glycosyl acceptors was found to lead exclusively to α-linked oligosaccharides. The observed exceptionally high α-selectivity was interpreted in terms of conformational changes in the glycosyl cation induced by the bulky 2-O-TIPS group.

show abstract

“…For this reason, in a recent synthesis of linear α(1→5)-linked oligoarabinofuranosides we had to synthesize a key building block 3a by a detour via thioglycoside (Scheme 1). 6h Here, we report that a monosaccharide with 4-(3-chloropropoxy)phenyl (CPP) aglycon (3b), which is a homolog of the known 6h glycoside 3a, can be easily synthesized (Scheme 1) by the reaction of orthoester 1 with 4-(3-chloropropoxy)phenol (CPP-OH, 2b 8 ). This became possible due to unusual fact that two homologous phenols 2a and 2b differing by only one methylene group in the side chain re- 9 3 6 -5 2 1 4 1 4 3 7 -2 0 9…”

mentioning

confidence: 99%

Length Matters: One Additional Methylene Group in a Reactant is Able to Affect the Reactivity Pattern and Significantly Increase the Product Yield

Stepanova

Podvalnyy

Abronina

et al. 2018

Synlett

View full text Add to dashboard Cite

The outcome of the nucleophilic opening of 3-O-benzoyl-β-d-arabinofuranose 1,2,5-orthobenzoate with 4-(ω-chloroalkoxy)phenols (SnCl4, CH2Cl2, –25 °C) unusually strongly depends on the length of the methylene chain of the nucleophile. The presence of one extra methylene group in the molecule of 4-(3-chloropropoxy)phenol [as compared to 4-(2-chloroetoxy)phenol] results in four-fold reduction in the reaction time and five-fold increase in the yield of a selectively protected monosaccharide glycoside with a hydroxy group at C-5, which is a valuable building block for the synthesis of oligoarabinofuranosides related to mycobacterial arabinans. Possible reasons and consequences of this finding are discussed.

show abstract

An efficient multigram-scale synthesis of 4-(ω-chloroalkoxy)phenols

Cited by 16 publications

References 36 publications

Black Swan in Phase Transfer Catalysis: Influence of Mixing Mode on the Stereoselectivity of Glycosylation

Black Swan in Phase Transfer Catalysis: Influence of Mixing Mode on the Stereoselectivity of Glycosylation

A Novel Glycosyl Donor with a Triisopropylsilyl Nonparticipating Group in Benzyl-Free Stereoselective 1,2-cis-Galactosylation

Length Matters: One Additional Methylene Group in a Reactant is Able to Affect the Reactivity Pattern and Significantly Increase the Product Yield

Contact Info

Product

Resources

About