Mild deprotection of PMB ethers using tert-butyl bromide

Rival, Nicolas; Grados, Arantxa Albornoz; Schiavo, Lucie; Colobert, Françoise; Hanquet, Gilles

doi:10.1016/j.tetlet.2015.10.067

Cited by 6 publications

(10 citation statements)

References 37 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…19 Following the general procedure using 5% ethyl acetate in hexanes as eluant, 2g was obtained as a white solid (86.5 mg, 89% yield); 1 H NMR (300 MHz, CDCl 3 ) δ 3.59 (tt, J = 10.6, 4.8 Hz, 1H), 1.96 (dt, J = 12.5, 3.4 Hz, 1H), 1.85−0.94 (m, 30H), 0.89 (d, J = 6.5 Hz, 3H), 0.87 (d, J = 1.4 Hz, 3H), 0.85 (d, J = 1.4 Hz, 3H), 0.80 (s, 3H), 0.64 (s, 3H); 13 5-(Benzyloxy)pentan-1-ol (2h). 20 Following the general procedure using 7% ethyl acetate in hexanes as eluant, 2h was obtained as a colorless liquid (34 mg, 70% yield); 1 H NMR (300 MHz, CDCl 3 ) δ 7. 40 20 Following the general procedure using 10% ethyl acetate in hexanes as eluant, 2i was obtained as a colorless liquid (32.5 mg, 89% yield); 1 H NMR (300 MHz, CDCl 3 ) δ 4.07 (t, J = 6.6 Hz, 2H), 3.66 (t, J = 6.4 Hz, 2H), 2.05 (s, 3H), 1.74− 1.59 (m, 4H), 1.51−1.35 (m, 2H); 13 C NMR (75 MHz, CDCl 3 ) δ 171.4, 64.6, 62.8, 32.4, 28.5, 22.4, 21.2.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…20 Following the general procedure using 7% ethyl acetate in hexanes as eluant, 2h was obtained as a colorless liquid (34 mg, 70% yield); 1 H NMR (300 MHz, CDCl 3 ) δ 7. 40 20 Following the general procedure using 10% ethyl acetate in hexanes as eluant, 2i was obtained as a colorless liquid (32.5 mg, 89% yield); 1 H NMR (300 MHz, CDCl 3 ) δ 4.07 (t, J = 6.6 Hz, 2H), 3.66 (t, J = 6.4 Hz, 2H), 2.05 (s, 3H), 1.74− 1.59 (m, 4H), 1.51−1.35 (m, 2H); 13 C NMR (75 MHz, CDCl 3 ) δ 171.4, 64.6, 62.8, 32.4, 28.5, 22.4, 21.2.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…6-Hydroxyhexyl Benzoate (2j). 20 Following the general procedure using 7% ethyl acetate in hexanes as eluant, 2j was obtained as a colorless liquid (41.2 mg, 74% yield); 1 H NMR (300 MHz, CDCl 3 ) δ 8.09−7.97 (m, 2H), 7.62−7.50 (m, 1H), 7.49−7.38 (m, 2H), 4.32 (t, J = 6.6 Hz, 2H), 3.65 (t, J = 6.5 Hz, 2H), 1.86−1.71 (m, 2H), 1.66− 1.37 (m, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ 166.8, 133.0, 130.5, 129.6, 128.5, 65.1, 62.9, 32.7, 28.8, 26.0, 25.5.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…5-((tert-Butyldiphenylsilyl)oxy)pentan-1-ol (2n). 20 Following the general procedure using 5% ethyl acetate in hexanes as eluant, 2n was obtained as a colorless liquid (74 mg, 86% yield); 1 H NMR (300 MHz, CDCl 3 ) δ 7.70−7.60 (m, 4H), 7.46−7.32 (m, 6H), 3.72−3.56 (m, 4H), 1.65−1.35 (m, 6H), 1.04 (s, 9H); 13 C NMR (75 MHz, CDCl 3 ) δ 135.7, 134.1, 129.6, 127.7, 63.9, 62.9, 32.5, 32.4, 27.0, 22.1, 19.3.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…tert-Butyl (3-Hydroxypropyl)carbamate (2o). 20 Following the general procedure using 20% ethyl acetate in hexanes as eluant, 2o was obtained as a colorless liquid (32 mg, 73% yield); 1 H NMR (300 MHz, CDCl 3 ) δ 4.78 (s, 1H), 3.65 (t, J = 5.7 Hz, 2H), 3.28 (q, J = 6.3 Hz, 2H), 1.65 (p, J = 5.8 Hz, 2H), 1.44 (s, 9H); 13 C NMR (75 MHz, CDCl 3 ) δ 157.4, 79.8, 59.3, 36.9, 33.1, 28.5.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

See 4 more Smart Citations

Oxidative Deprotection ofp-Methoxybenzyl Ethers via Metal-Free Photoredox Catalysis

2019

View full text Add to dashboard Cite

An efficient and greener deprotection method for p-methoxybenzyl (PMB) ethers using a metal-free visible light photoredox catalyst and air and ammonium persulfate as the terminal oxidants is presented. Various functional groups and protecting groups were tolerated in the developed method to achieve good to excellent yields in short reaction times. Significantly, the developed method was compatible with PMB ethers derived from primary, secondary, and tertiary alcohols and a gram-scale reaction. Mechanistic studies support a proposed reaction mechanism that involves single electron oxidation of the PMB ether.

show abstract

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

See 3 more Smart Citations

Oxidative Deprotection ofp-Methoxybenzyl Ethers via Metal-Free Photoredox Catalysis

2019

View full text Add to dashboard Cite

show abstract

ChemInform Abstract: Mild Deprotection of PMB Ethers Using tert‐Butyl Bromide.

et al. 2016

View full text Add to dashboard Cite

Mild Deprotection of PMB Ethers Using tert-Butyl Bromide. -A mild method for the cleavage and scavenging of 4-methoxybenzyl protecting group using tBuBr is reported. Under the reaction conditions, other protecting groups such as acid sensitive allyl, benzyl, and silyl-ethers or isopropylidene acetals are unchanged. Interestingly, a selective alkoxy-Pmb cleavage is observed in the presence of a Pmb-phenoxy ether. -(RIVAL, N.; ALBORNOZ GRADOS, A.; SCHIAVO, L.; COLOBERT, F.; HANQUET*, G.; Tetrahedron Lett. 56 (2015) 49, 6823-6826, http://dx.

show abstract

p-Chlorobenzyl Ether: A p-Methoxybenzyl Ether in Disguise

2016

View full text Add to dashboard Cite

In the chemistry of polyfunctionalized organic compounds, protecting groups that can undergo mild and selective cleavage while still being stable during the entire synthetic sequence are often required. In this work, we present a straightforward conversion of the robust p-chlorobenzyl ether into the more labile and well-described p-methoxybenzyl ether using palladium catalysis. This reaction was demonstrated to be high yielding and compatible with a wide range of functionalities, thereby providing a useful supplement to the conventional ether protecting groups.

show abstract

Mild deprotection of PMB ethers using tert-butyl bromide

Cited by 6 publications

References 37 publications

Oxidative Deprotection ofp-Methoxybenzyl Ethers via Metal-Free Photoredox Catalysis

Oxidative Deprotection ofp-Methoxybenzyl Ethers via Metal-Free Photoredox Catalysis

ChemInform Abstract: Mild Deprotection of PMB Ethers Using tert‐Butyl Bromide.

p-Chlorobenzyl Ether: A p-Methoxybenzyl Ether in Disguise

Contact Info

Product

Resources

About