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Baeyer-Villiger Oxidation Catalysts

  • School of Engineering/Graduate School of Engineering
  • Department of Molecular and Macromolecular Chemistry
  • Research Group of Molecular Chemistry
  • (Laboratory of Catalysis in Organic Synthesis)

Kazuaki Ishihara [Professor]

http://www.ishihara-lab.net/english/

  • School of Engineering/Graduate School of Engineering
  • Department of Molecular and Macromolecular Chemistry
  • Research Group of Molecular Chemistry
  • (Laboratory of Catalysis in Organic Synthesis)

Muhammet Uyanik [Assistant Professor]

Outline of Seeds

BaeyerVilliger (BV) oxidation is one of the most important transformations in organic synthesis, since valuable lactones or esters can be obtained directly from the corresponding ketones. We have developed a highly efficient and selective LiB(C6F5)4 or Ca[B(C6F5)4]2-catalyzed BV oxidation of various cycloalkanones with 30%-wt aqueous hydrogen peroxide to give the corresponding lactones or esters in high yield. Additionally, we have found that the reaction rate is accelerated with the use of oxalic acid as a co-catalyst. Moreover, beta-silyl cyclohexanones can be oxidized to the corresponding unsaturated carboxylic acids or hydroxylactones in high yields via BV oxidation/beta-elimination reaction sequences and subsequent epoxidation/cyclization reaction sequences, by controlling the amounts of hydrogen proxide and oxalic acid. These reactions proceed under mild conditions and tolerate various functional groups.

Novelty and originality of this research

In contrast to conventional acid catalysts, fluorinated tetraarylborate salts of the alkali or alkaline-earth metals are highly lipophilic and exhibit efficient and selective catalytic activity for BV oxidation with aqueous hydrogen peroxide under biphasic conditions. The catalyst loading could be reduced to 1 or even 0.01 mol% [turnover number (TON) of the catalyst = 10000]. The oxidation reactions proceed under mild conditions, and several functional groups such as terminal or internal alkenyl, hydroxy, acetoxy, silyloxy, and halo groups are tolerated under the present conditions. Moreover, the success of the catalytic BV oxidation of -silyl cyclohexanones with hydrogen peroxide in place of m-CPBA led to the development of unique oxidative cascade reactions.

Application and research area for Industry collaboration

Synthesis of lactones or esters

Key Takeaway

Highly efficient BayerVilliger oxidation catalysts for the synthesis of lactone or ester

Keywords

lactone, ester, BayerVilliger oxidation, aqueous hydrogen peroxide, alkali metals, alkaline earth metals, borate salt,

Technologies

  • Synthetic method of lactones and esters

Patents

  • JP5920889(B2)

Monographs, Papers and Articles

  • M. Uyanik, D. Nakashima, K. Ishihara, Angew. Chem. Int. Ed. 2012, 51(36), 9093–9096.
  • M. Uyanik, K. Ishihara, ACS Catal. 2013, 3(4), 513–520.