100 Years of Baeyer–Villiger Oxidations

Renz, Michael; Meunier, Bernard

doi:10.1002/(sici)1099-0690(199904)1999:4<737::aid-ejoc737>3.0.co;2-b

Cited by 542 publications

(338 citation statements)

References 99 publications

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“…Because the Baeyer-Villager (B-V) reaction is known to be mediated (62) by oxidative enzymes (e.g., cytochrome P450), which are present in the nasopharyngeal mucus layer (2,32,63,64), and the B-V reaction of deuterated cyclic ketones forming deuterated lactones is known to show an isotope effect (62), such a reaction might affect odor perception of pairs such as 1 and 1-d 28 . Indeed, we have confirmed that 1-d 28 undergoes peracid-mediated B-V oxidation faster than nondeuterated 1, in accord with literature results (62), although a full kinetic analysis in the case of 1/1-d 28 was not possible due to partial overlap of ketone and lactone peaks under GC-MS conditions.…”

Section: Response Of a Human Musk Or To Deuterated And Nondeuteratedmentioning

confidence: 99%

Implausibility of the vibrational theory of olfaction

Block

Jang

Matsunami

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

115

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The vibrational theory of olfaction assumes that electron transfer occurs across odorants at the active sites of odorant receptors (ORs), serving as a sensitive measure of odorant vibrational frequencies, ultimately leading to olfactory perception. A previous study reported that human subjects differentiated hydrogen/ deuterium isotopomers (isomers with isotopic atoms) of the musk compound cyclopentadecanone as evidence supporting the theory. Here, we find no evidence for such differentiation at the molecular level. In fact, we find that the human musk-recognizing receptor, OR5AN1, identified using a heterologous OR expression system and robustly responding to cyclopentadecanone and muscone, fails to distinguish isotopomers of these compounds in vitro. Furthermore, the mouse (methylthio)methanethiol-recognizing receptor, MOR244-3, as well as other selected human and mouse ORs, responded similarly to normal, deuterated, and 13 C isotopomers of their respective ligands, paralleling our results with the musk receptor OR5AN1. These findings suggest that the proposed vibration theory does not apply to the human musk receptor OR5AN1, mouse thiol receptor MOR244-3, or other ORs examined. Also, contrary to the vibration theory predictions, muscone-d 30 lacks the 1,380-to 1,550-cm −1 IR bands claimed to be essential for musk odor. Furthermore, our theoretical analysis shows that the proposed electron transfer mechanism of the vibrational frequencies of odorants could be easily suppressed by quantum effects of nonodorant molecular vibrational modes. These and other concerns about electron transfer at ORs, together with our extensive experimental data, argue against the plausibility of the vibration theory.olfaction | isotopomers | cyclopentadecanone | muscone | electron transfer I n 1870, the British physician William Ogle wrote: "As in the eye and the ear the sensory impression is known to result not from the contact of material particles given off by the object seen or heard, but from waves or undulations of the ether or the air, one cannot but suspect that the same may be true in the remaining sense, and that the undulatory theory of smell. . . [may be] the true one" (1, 2). Of the 29 different "theories of odour" listed in the 1967 edition of The Chemical Senses (3), nine associate odor with vibrations, particularly those theories championed by Dyson (4, 5) and Wright (6-8). However, the premise that olfaction involves detection of vibrational frequencies of odorants remains highly speculative because neither the structures of the odorant receptors (ORs) nor the binding sites or the activation mechanisms triggered upon odorant binding to ORs have been established. In 1996-1997, Turin (9-12) elaborated on the undulatory theory of smell, as considered in more detail below, and suggested that a mechanism analogous to inelastic electron tunneling spectroscopy (13) may be involved, where tunneling electrons in the receptor probe the vibrational frequencies of odorants. In 2013, Gane et al. (14) In judging the plausibility...

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Section: Response Of a Human Musk Or To Deuterated And Nondeuteratedmentioning

confidence: 99%

Implausibility of the vibrational theory of olfaction

Block

Jang

Matsunami

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

115

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“…As a result, acid 2a was obtained with 91 % yield. Based on the Baeyer-Villiger oxidation mechanism [2][3][4][5][6] it is possible to believe that the performic acid reacts with 2-formyloxycyclododecanone 5 to form ether 10 (R = H). Consequently, isolation of 2a with high yield upon oxidation of 5 confirms the ability of ether 10 to be oxidized with formation of acid 2a.…”

Section: R Can Be = H Me Hc=o O=c (H) Omentioning

confidence: 99%

“…The Baeyer-Villiger reaction [1][2][3][4][5][6], known already for more than a century, has found wide application in synthesis of lactones and ω-hydroxycarboxylic acids. The oxidation of acetals (obtained from cyclic ketones) under action of peracids was investigated in a small number of works [7][8][9][10][11].…”

Section: Introductionmentioning

confidence: 99%

New transformation of cycloalkanone acetals by peracids α,ω-dicarboxylic acids synthesis

Terent’ev

Chodykin

2005

Open Chemistry

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“…Although several reviews on the BV reactions have been published, which covers the development of the BV oxidation, the concerned oxidants, corresponding catalysts, etc. [27,28], no review aiming at the specific Sn-based catalysts for BV oxidation by using H2O2 as oxidant was published.…”

Section: Introductionmentioning

confidence: 99%

Sn-based catalysts for Baeyer-Villiger oxidations by using hydrogen peroxide as oxidant

Cui

Shi

2016

Sci. China Mater.

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Baeyer-Villiger (BV) oxidation is one of the most important transformation reactions in synthetic organic chemistry. Catalytic versions of the BV oxidation are particularly attractive in practical applications, because the catalytic transformation substantially simplifies reaction process while minimizing reactant consumption as well as waste production. Further benefits are expected from replacing peracids, the traditionally used oxidant, by low cost and environmentally friendly hydrogen peroxide (H2O2). This review will first introduce very briefly the features of BV oxidation reactions, and the corresponding oxidants traditionally used. Afterwards, the emphasis will be placed on the specific Sn-based catalysts, their performance comparison for the BV oxidation reaction by using H2O2 as oxidant, and the catalytic mechanisms of most Sn-based catalysts reported so far, including homogeneous Sn-based catalysts (such as Sn-based fluorous biphase system catalysts), heterogeneous Sn-based catalysts (such as Sn-based zeolite catalysts, Sn-based mesoporous composites, Sn-incorporated clay catalysts, Sn-based metal oxide composites and polymer supported Sn catalysts). Finally, the Sn-based catalysts for BV oxidation are outlooked for their potentials and perspectives in enhancing the performance and then accelerating the practical applications of BV oxidations by using H2O2. The developing direction of the Sn-based catalytic BV reaction is also illustrated.

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100 Years of Baeyer–Villiger Oxidations

Cited by 542 publications

References 99 publications

Implausibility of the vibrational theory of olfaction

Implausibility of the vibrational theory of olfaction

New transformation of cycloalkanone acetals by peracids α,ω-dicarboxylic acids synthesis

Sn-based catalysts for Baeyer-Villiger oxidations by using hydrogen peroxide as oxidant

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