Asymmetric synthesis of tetronic acids by Blaise reaction of protected optically active cyanohydrins

Duffield, Jonathan J.; Regan, Andrew C.

doi:10.1016/0957-4166(96)00059-6

Cited by 34 publications

(9 citation statements)

References 19 publications

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“…Cyanohydrins are expedient starting materials and valuable key building blocks for the preparation and one step synthesis of several classes of compounds such as α-hydroxy-carboxylic acids [1][2][3][4][5][6][7] which play a vital role in organic synthesis [8][9][10]. Optically active cyanohydrins are also versatile intermediates in organic synthesis and have received considerable amount of *Corresponding author.…”

Section: Introductionmentioning

confidence: 99%

Preparation and reactions of optically active cyanohydrins using the (R)-hydroxynitrile lyase from Prunus amygdalus

Yosef

Morsy

Mahran

et al. 2007

JICS

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Cyanuration of 2-naphthaldehyde (1) and 5-methyl-2-furaldehyde (2) yielded the racemic 2-hydroxy-2-(β-naphthyl)ethanenitrile (R,S)-3 and 2-hydroxy-2-(5-methyl-2-furyl)ethanenitrile (R,S)-5, respectively. The same reaction can be completed by using acetone cyanohydrin (4) as a transcyanating agent. The optically active (R)-3 and (S)-5 could be respectively obtained by hydrocyanation of 1 and 2 using (R)-hydroxynitrile lyase (R)-PaHNL [EC 4.1.2.10] from almonds (Prunus amygdalus) as a chiral catalyst. Cyanohydrins 3 and 5 in their racemic and optically active forms undergo a number of transformations which involve either the hydroxyl group or the cyanide function. Moreover, derivatization of 3 and 5 with (S)-Naproxen ® chloride (S)-14 gave the respective diastereoisomers. The optical activity of (R)-3 and (S)-5 as well as their derivatives were recorded. The postulated structures for the new products were supported with compatible elementary and spectroscopic (IR, 1 H NMR, 13 C NMR, MS, and single crystal X-Ray crystallography) analyses. The antimicrobial activity of some selected racemic new products and their respective optically active analogues were also undertaken.

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Section: Introductionmentioning

confidence: 99%

Preparation and reactions of optically active cyanohydrins using the (R)-hydroxynitrile lyase from Prunus amygdalus

Yosef

Morsy

Mahran

et al. 2007

JICS

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“…In addition, they are also quite useful in some organic syntheses4,, 5 and various asymmetric transformations6,, 7 due to the activated functional groups and the presence of an asymmetric carbon in the molecule. Therefore studies of the synthesis and properties of γ‐butyrolactones and their derivatives have recently attracted much attention 8–10. We have designed a convenient synthetic route by using the anti ‐addition reaction of bromine, and obtained a group of highly functionalized γ‐butyrolactones.…”

Section: Methodsmentioning

confidence: 99%

Mass spectrometric study of ?-aryl-?,�?-diethoxy-?, ?-butenolides

Wang¹,

Wang²,

He³

2000

Rapid Commun. Mass Spectrom.

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Electron impact mass spectra of eight of the title compounds are reported. Abundant fragment ions were produced under electron impact (EI) conditions and, with one exception, the ($¿hbox¿ArC¿¿equiv$ O) ions were the base peaks. The EI fragmentation mechanisms of two representative compounds were studied with the aid of high-resolution and mass-analyzed ion kinetic energy spectrometry (MIKES) data. The M(+) ions fragment to give both an odd-electron ion and an even-electron fragment ion. Two H-atom rearrangements proceeding via four-membered ring intermediates and three losses of CO through i- and alpha-fragmentations were observed under EI. On comparing fragmentations under EI conditions with those under FAB conditions for two of the compounds, the fragmentation mechanisms were reasonably similar, with additional fragmentations rationalized in terms of the ionization proton being located on the oxygen atom of the beta-ethoxy group.

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“…[5] For example, (2R,3E)-2-hydroxypent-3-enenitrile (1), derived from crotonaldehyde and HCN can be prepared in 99 % enantiomeric purity by using either purified paHNL [6] or defatted almond meal containing the enzyme (Scheme 1). [10] The protected forms can be used to produce chiral nitrones, [11] cyclic 1,2-ethanolamines, [12] chiral piperidinols, [12] α-hydroxy-β-amino acids, [13] tetronic acids [14] and 1,2-ethanolamines. In the unprotected form it has been used in the synthesis of α-hydroxy esters, [8] α-hydroxy acids [9] and vicinal diols.…”

Section: Introductionmentioning

confidence: 99%

“…tert-Butyl (2R,3S,4R,5S)-2-(Benzyloxymethyl)-3,4-O-isopropylidene-5-hydroxypiperidine-1-carboxylate(14): A solution of TBAF in THF (1 m, 2.60 mL, 2.60 mmol) was added to a solution of the above TBDPS ether (764 mg, 1.21 mmol) in THF(15 mL). After 2 h, TLC analysis revealed complete conversion.…”

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confidence: 99%

Synthesis of Eight 1‐Deoxynojirimycin Isomers from a Single Chiral Cyanohydrin

et al. 2012

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Eight configurational 1‐deoxynojirimycin isomers have been synthesized starting from a chiral cyanohydrin as the common precursor. The cyanohydrin chiral pool building block is easily accessible in large quantities by using almond hydroxynitrile lyase as the chiral catalyst in condensing hydrogen cyanide and crotonaldehyde. Our work complements the large body of literature on the synthesis of 1‐deoxynojirimycin derivatives with the distinguishing feature that eight stereoisomers of this important class of glycosidase inhibitors can be derived from a common precursor in an efficient manner.

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Asymmetric synthesis of tetronic acids by Blaise reaction of protected optically active cyanohydrins

Cited by 34 publications

References 19 publications

Preparation and reactions of optically active cyanohydrins using the (R)-hydroxynitrile lyase from Prunus amygdalus

Preparation and reactions of optically active cyanohydrins using the (R)-hydroxynitrile lyase from Prunus amygdalus

Mass spectrometric study of ?-aryl-?,�?-diethoxy-?, ?-butenolides

Synthesis of Eight 1‐Deoxynojirimycin Isomers from a Single Chiral Cyanohydrin

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