The mechanism of the first step of the Mitsunobu reaction

Camp, David Brian; Itzstein, Mark von; Jenkins, Ian D.

doi:10.1016/j.tet.2015.05.099

Cited by 22 publications

(27 citation statements)

References 22 publications

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“…Does the reaction of the ethyl 2-arylazocarboxylates with triphenylphosphine form Morrison–Brunn–Huisgen betaine intermediates 27 like in the typical Mitsunobu reaction? Precedent mechanistic studies indicate the formation of betaine intermediates from azo reagents and phosphines.…”

Section: Resultsmentioning

confidence: 99%

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Advances and mechanistic insight on the catalytic Mitsunobu reaction using recyclable azo reagents

et al. 2016

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Section: Resultsmentioning

confidence: 99%

“…In light of the electron density of a nitrogen atom, these chemical shifts are roughly consistent with that of di- 15 N-DEAD (+44.2 ppm) and DEAD (+44.8 ppm). 27 …”

Section: Resultsmentioning

confidence: 99%

Advances and mechanistic insight on the catalytic Mitsunobu reaction using recyclable azo reagents

et al. 2016

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“…The corresponding ( R , S / S , R ) enantiomers were synthesized as shown in Scheme by using a Mitsunobu reaction to invert the stereochemistry at the α‐position of the side chain . Enantiomer 8 b was protected by reaction with tert ‐butyldimethylsilyl chloride (TBSCl) in the presence of imidazole to afford intermediate 10 .…”

Section: Resultsmentioning

confidence: 99%

“…The corresponding( R,S/S,R)e nantiomers were synthesized as shown in Scheme 3b yu sing aM itsunobu reactiont oi nvert the stereochemistry at the a-position of the side chain. [55][56] Enantiomer 8b was protected by reaction with tert-butyldimethylsilyl chloride (TBSCl) in the presence of imidazole to afford intermediate 10.M itsunobur eactiono f10 followed by hydrolysis of the resultingb enzoate in situ provided compound 11 containing the inverted a-hydroxyl group. [56] Removal of the TBS group with tetra-n-butylammonium fluoride (TBAF) led to diol 12 and subsequenth ydrogenolysis of the benzylg roup with Pd/C in EtOH providede nantiomerically enriched compound 13.T he complete transformation of starting (S,S)-enantiomer 8b into (R,S)-compound 13 was confirmed by NMR spectroscopic analysis,w hichs howedade > 99 %a nd an overall yield of 78 %f or the four-step process.…”

Section: Asymmetrics Ynthesis Of B-o-4 Lignin Model Dimersmentioning

confidence: 99%

Enantioselective Syntheses of Lignin Models: An Efficient Synthesis of β‐O‐4 Dimers and Trimers by Using the Evans Chiral Auxiliary

Njiojob

Bozell

Long

et al. 2016

Chemistry A European J

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We describe an efficient five-step, enantioselective synthesis of (R,R)- and (S,S)-lignin dimer models possessing a β-O-4 linkage, by using the Evans chiral aldol reaction as a key step. Mitsunobu inversion of the (R,R)- or (S,S)-isomers generates the corresponding (R,S)- and (S,R)-diastereomers. We further extend this approach to the enantioselective synthesis of a lignin trimer model. These lignin models are synthesized with excellent ee (>99 %) and high overall yields. The lignin dimer models can be scaled up to provide multigram quantities that are not attainable by using previous methodologies. These lignin models will be useful in degradation studies probing the selectivity of enzymatic, microbial, and chemical processes that deconstruct lignin.

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“…In 1981, Mitsunobu published a first review about this reaction, entitled "The Use of Diethyl Azodicarboxylate and Triphenylphosphine in Synthesis and Transformation of Natural Products" [ 2 ]. Thereafter, several further general reviews have appeared [ 3 – 6 ], owing to the spectacular development of diversified synthetic applications of the Mitsunobu reaction, whilst the long term debate about the mechanism of this reaction was still ongoing [ 7 – 12 ].…”

Section: Introductionmentioning

confidence: 99%

Anomeric modification of carbohydrates using the Mitsunobu reaction

Hain¹,

Rollin²,

Klaffke³

et al. 2018

Beilstein J. Org. Chem.

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The Mitsunobu reaction basically consists in the conversion of an alcohol into an ester under inversion of configuration, employing a carboxylic acid and a pair of two auxiliary reagents, mostly triphenylphosphine and a dialkyl azodicarboxylate. This reaction has been frequently used in carbohydrate chemistry for the modification of sugar hydroxy groups. Modification at the anomeric position, leading mainly to anomeric esters or glycosides, is of particular importance in the glycosciences. Therefore, this review focuses on the use of the Mitsunobu reaction for modifications of sugar hemiacetals. Strikingly, unprotected sugars can often be converted regioselectively at the anomeric center, whereas in other cases, the other hydroxy groups in reducing sugars have to be protected to achieve good results in the Mitsunobu procedure. We have reviewed on the one hand the literature on anomeric esterification, including glycosyl phosphates, and on the other hand glycoside synthesis, including S- and N-glycosides. The mechanistic details of the Mitsunobu reaction are discussed as well as this is important to explain and predict the stereoselectivity of anomeric modifications under Mitsunobu conditions. Though the Mitsunobu reaction is often not the first choice for the anomeric modification of carbohydrates, this review shows the high value of the reaction in many different circumstances.

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The mechanism of the first step of the Mitsunobu reaction

Cited by 22 publications

References 22 publications

Advances and mechanistic insight on the catalytic Mitsunobu reaction using recyclable azo reagents

Advances and mechanistic insight on the catalytic Mitsunobu reaction using recyclable azo reagents

Enantioselective Syntheses of Lignin Models: An Efficient Synthesis of β‐O‐4 Dimers and Trimers by Using the Evans Chiral Auxiliary

Anomeric modification of carbohydrates using the Mitsunobu reaction

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