- SYNTHESIS OF DEUTERATED ALDEHYDES
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Described are methods for preparing a deuterated aldehyde using N-heterocyclic carbene catalysts in a solvent comprising D2O. The methods may be used to convert a wide variety of aldehydes (e.g., aryl, alkyl, or alkenyl aldehydes) to C-1 deuterated aldehydes under mild reaction conditions without functionality manipulation.
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Paragraph 0008; 0084
(2021/03/13)
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- N-Heterocyclic Carbene Catalyzed Deuteration of Aldehydes in D 2 O
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An N-heterocyclic carbene (NHC)-catalyzed direct deuteration of aldehydes in a mixed solvent of deuterium oxide (D 2 O) and cyclopentyl methyl ether was established. The present deuteration is possibly initiated by the formation of a Breslow intermediate from the aldehyde and the NHC, with subsequent trapping by D 2 O providing the monodeuterated aldehyde.
- Miki, Yuya,Sajiki, Hironao,Sawama, Yoshinari
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p. 699 - 702
(2020/04/07)
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- Formyl-selective deuteration of aldehydes with D2O: Via synergistic organic and photoredox catalysis
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Formyl-selective deuteration of aldehydes is of high interest for labeling purposes and for optimizing properties of drug candidates. Herein, we report a mild general method for formyl-selective deuterium labeling of aldehydes with D2O, an inexpensive deuterium source, via a synergistic combination of light-driven, polyoxometalate-facilitated hydrogen atom transfer and thiol catalysis. This highly efficient, scalable reaction showed excellent deuterium incorporation, a broad substrate scope, and excellent functional group tolerance and selectivity and is therefore a practical method for late-stage modification of synthetic intermediates in medicinal chemistry and for generating libraries of deuterated compounds.
- Dong, Jianyang,Wang, Xiaochen,Wang, Zhen,Song, Hongjian,Liu, Yuxiu,Wang, Qingmin
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p. 1026 - 1031
(2020/02/11)
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- Visible light driven deuteration of formyl C-H and hydridic C(sp3)-H bonds in feedstock chemicals and pharmaceutical molecules
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Deuterium labelled compounds are of significant importance in chemical mechanism investigations, mass spectrometric studies, diagnoses of drug metabolisms, and pharmaceutical discovery. Herein, we report an efficient hydrogen deuterium exchange reaction u
- Cao, Hui,Chen, Wei,Chew, Junhong,Kuang, Yulong,Shi, Xiangcheng,Tang, Haidi,Wu, Jie
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p. 8912 - 8918
(2020/09/09)
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- Deoxygenative Deuteration of Carboxylic Acids with D2O
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We report a general, practical, and scalable means of preparing deuterated aldehydes from aromatic and aliphatic carboxylic acids with D2O as an inexpensive deuterium source. The use of Ph3P as an O-atom transfer reagent can facilitate the deoxygenation of aromatic acids, while Ph2POEt is a better O-atom transfer reagent for aliphatic acids. The highly precise deoxygenation of complex carboxylic acids makes this protocol promising for late-stage deoxygenative deuteration of natural product derivatives and pharmaceutical compounds.
- Zhang, Muliang,Yuan, Xiang-Ai,Zhu, Chengjian,Xie, Jin
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supporting information
p. 312 - 316
(2018/11/25)
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- Method for preparing deuterated aldehyde from carboxylic acid using iridium complex as catalyst under irradiation of blue light
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A method for preparing deuterated aldehyde from carboxylic acid using an iridium complex as a catalyst under the irradiation of blue light is as follows: aromatic carboxylic acid (ArCOOH) used as a raw material and triphenylphosphine used as a deoxidizing agent are irradiated by blue light in a solution of dichloromethane and heavy water, in the atmosphere of argon, under the condition of dipotassium phosphate used as alkali and using [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 as a photocatalyst and thiophenol 2,4,6-triisopropylbenzenethiol as an organic small molecule catalyst to obtain a deuterated aromatic aldehyde compound; or aliphatic carboxylic acid (Alk-COOD) used as the raw material and diphenylethoxyphosphine used as a deoxidizing agent are irradiated by blue light in a solution of toluene, inthe atmosphere of argon and under the condition of 2,6-lutidine used as alkali to obtain a deuterated fatty aldehyde compound.
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Paragraph 0033
(2019/02/13)
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- Chirally deuterated benzyl chlorides from benzyl alcohols via hexachloroacetone/polymer-supported triphenylphosphine: Synthesis of protected (2S, 3S)-[3-2H, 15N]-tyrosine
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Chirally deuterated benzyl chlorides were prepared using novel, general hexachloroacetone/polymer-supported triphenylphosphine treatment of chirally deuterated benzyl alcohols. Doubly labeled protected tyrosine was obtained in 62% yield with 86% de at the α-carbon and 82% de at the β-carbon. Key in the synthesis was the alkylation of 15N-labeled (-)-8-phenylmenthylhippurate with R-(-)-4-triisopropylsilyloxybenzyl-α-d chloride. Chirally deuterated benzyl chlorides were prepared in high yield with inversion from benzyl alcohols using solid-phase methods. One of the benzyl chlorides obtained was used in the synthesis of protected tyrosine labeled with 15N and chirally deuterated on the β-position. Copyright
- Barnett, Derek W.,Refaei, Maryanne S.,Curley Jr., Robert W.
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- Norlignan biosynthesis in Asparagus officinalis L.: The norlignan originates from two non-identical phenylpropane units
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Little is known about the biosynthetic mechanism(s) of norlignans with C6-C5-C6 skeletons in spite of their important contributions to heartwood formation in conifers. To clarify the mechanism(s), we have established cell-
- Suzuki,Umezawa,Shimada
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p. 3252 - 3257
(2007/10/03)
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- Isoflavonoid Biosynthesis: Concerning the Aryl Migration
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Feeding experiments with 13C- or 2H-labelled precursors in CuCl2-treated red clover (Trifolium pratense) seedings have demonstrated that the isoflavone formononetin (6) and the pterocarpan phytoalexins medicarpin (10) and maackiain (11) are biosynthesized
- Al-Ani, Hakim A. M.,Dewick, Paul M.
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p. 2831 - 2838
(2007/10/02)
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