Reaction of the acetals with TESOTf-base combination; speculation of the intermediates and efficient mixed acetal formation

Journal of the American Chemical Society
Hiromichi FujiokaYasuyuki Kita

Abstract

We report here unexpected highly chemoselective deprotection of the acetals from aldehydes. Treatment of acetal compounds from aldehydes with TESOTf-2,6-lutidine or TESOTf-2,4,6-collidine in CH2Cl2 at 0 degrees C followed by H2O workup at the same temperature caused the conversion of the acetal functions to aldehyde functions. The reaction had generality and was applied to many acetal compounds. Study using various bases revealed the reaction and reached the best combination of TESOTf-base. It was very mild and highly chemoselective and proceeded under weakly basic conditions. Then, many functional groups such as allyl alcohol, silyl ether, acetate, methyl ether, triphenylmethyl (Tr) ether, 1,3-dithiolane, methyl ester, and tert-butyl ester could survive under these conditions. Furthermore, this methodology could selectively deprotect the acetals in the presence of ketals as the most characteristic feature, although this chemoselectivity is difficult to achieve by other previously reported methods. A detailed study of the reaction including MS and NMR studies revealed the reaction mechanism for determining the structures of the intermediates, pyridinium-type salts. These intermediates had a weak electrophilicity and were succes...Continue Reading

References

Sep 24, 2004·Journal of the American Chemical Society·Hiromichi FujiokaYasuyuki Kita

❮ Previous
Next ❯

Citations

May 8, 2010·Chemical Communications : Chem Comm·Hiromichi FujiokaTomohiro Maegawa
Aug 5, 2011·Chemical Communications : Chem Comm·Hiromichi FujiokaTomohiro Maegawa
Jan 7, 2014·Chemical & Pharmaceutical Bulletin·Kenzo Yahata, Hiromichi Fujioka
Nov 5, 2016·Organic Letters·Naoki YasukawaYoshinari Sawama
Apr 14, 2017·The Journal of Organic Chemistry·Jogula SrinivasMasahiko Hayashi
Dec 20, 2014·Chemistry : a European Journal·Sebastian Wünsch, Bernhard Breit
Jan 5, 2017·Chemical & Pharmaceutical Bulletin·Reiya Ohta, Hiromichi Fujioka
Jul 8, 2017·Chemistry : a European Journal·Naoki YasukawaYoshinari Sawama
May 29, 2012·Chemistry, an Asian Journal·Hiromichi FujiokaKenichi Murai
Oct 16, 2018·Angewandte Chemie·Lin YangRan Hong
Oct 2, 2007·Chemistry : a European Journal·Hiromichi FujiokaYasuyuki Kita
May 15, 2013·Angewandte Chemie·Stephen HoJames L Leighton
Oct 2, 2020·Chemical & Pharmaceutical Bulletin·Hiromichi Fujioka
Dec 16, 2017·Chemical Communications : Chem Comm·Takahiro KawajiriYoshinari Sawama
Apr 4, 2018·Nature Chemical Biology·Michael M GaschlerBrent R Stockwell
Jul 26, 2012·Chemistry : a European Journal·Akihiro GotoHiromichi Fujioka
Dec 4, 2019·Angewandte Chemie·Hugo Quintela-VarelaDirk Trauner
Jan 22, 2011·Chemistry, an Asian Journal·Kenji SasakiMasayuki Inoue
Jun 30, 2011·Organic & Biomolecular Chemistry·Tomohiro MaegawaHiromichi Fujioka
Sep 19, 2020·Angewandte Chemie·Saskia SchulthoffAlois Fürstner
Oct 14, 2009·Organic Letters·Hiromichi FujiokaTomohiro Maegawa
Oct 31, 2009·Organic Letters·Michael R GesinskiScott D Rychnovsky
Sep 25, 2007·The Journal of Organic Chemistry·Hiromichi FujiokaYasuyuki Kita
Jan 22, 2010·The Journal of Organic Chemistry·Michael KrayerJonathan S Lindsey
Feb 6, 2008·Organic Letters·Michael J Gallen, Craig M Williams
Jul 31, 2013·Organic Letters·Stephen HanessianHelge Menz
Feb 13, 2019·The Journal of Organic Chemistry·Takahiro KawajiriYoshinari Sawama
Aug 27, 2019·Journal of the American Chemical Society·Xirui HuThomas J Maimone
May 30, 2014·The Journal of Organic Chemistry·Takashi OkitsuAkimori Wada
Sep 24, 2019·Organic Letters·Andrei V IosubJoakim Bergman
Mar 14, 2018·Chemical Reviews·Farzad SeidiDaniel Crespy
Mar 12, 2013·Journal of the American Chemical Society·Wanxiang ZhaoJianwei Sun

❮ Previous
Next ❯

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.