Addition of a Chiral Copper Reagent Derived from Propargylic Oxazolidininone to Aldehydes

Alouane, Nacira; Bernaud, Frederic; Marrot, Jérôme; Vrancken, Emmanuel; Mangeney, Pierre

doi:10.1021/ol0522743

Cited by 25 publications

(12 citation statements)

References 19 publications

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“…Vrancken and Mangeney 77 found that lithiated allemamides generated from the propargyl amide 228 could undergo aldol reactions in the presence of CuCN to afford anti -homopropargyl amino alcohols 241 with high yields and diastereoselectivities (Scheme 68). In most cases, the addition proceeds through the favored transition state anti a 241 .…”

Section: Reactions Of Allenamidesmentioning

confidence: 99%

Allenamides: A Powerful and Versatile Building Block in Organic Synthesis

et al. 2013

Chem. Rev.

321

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Section: Reactions Of Allenamidesmentioning

confidence: 99%

Allenamides: A Powerful and Versatile Building Block in Organic Synthesis

et al. 2013

Chem. Rev.

321

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“…Finally, a chiral version of this reaction could be proposed, starting from an enantiopure propargylic oxazolidinone. 7 As shown in Tables 1 and 2, the anti/syn ratio (ca. 95:5), seems to be more or less insensitive to the nature of the aldehyde, with the exception of butanal (R 2 = n-Pr, Table 2), which reacts with the cyanocuprates derived from propargylic ethers 4a-c to give the homopropargylic alcohols 5 in an anti/syn ratio of only 90:10.…”

Section: Preparation Of Anti-12-disubstituted Homopropargylic Alcohomentioning

confidence: 88%

Preparation of anti-1,2-Disubstituted Homopropargylic Alcohols by Addition of Allenyl(cyano)cuprates to Aldehydes

Alouane¹,

Vrancken²,

Mangeney³

2007

Synthesis

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“…The lithiation can be performed with s-BuLi at −78 • C and the amino alkyllithium can be trapped with electrophiles and undergoes conjugate addition to α,β-unsaturated carbonyls upon transmetallation with Cu salts (Scheme 7.39). N-propargyl oxazolidinones are also easily lithiated α to nitrogen to furnish useful synthetic intermediates that can be trapped with a range of electrophiles [52]. The lithiation of the chiral oxazolidinone 18 leads to the propargyllithium intermediates 18-Li, whose real structure remains unknown, and could be in equilibrium with the corresponding allenyllithium 19-Li that reacts with an aldehyde to furnish almost exclusively the corresponding allenic alcohol 20.…”

Section: Lithiation Of Acyclic Aminesmentioning

confidence: 99%

Nitrogen‐Bearing Lithium Compounds in Modern Synthesis

Degennaro¹,

Musio²,

Luisi³

2014

Lithium Compounds in Organic Synthesis

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IntroductionNitrogen-containing compounds are ubiquitous and are extremely important in synthesis. This chapter reports some general aspects of the generation, structure, and reactivity of nitrogen-bearing organolithiums showing the progress made over the last decade. The chapter does not cover comprehensively the field but the aim is to provide the reader with useful information on the generation, reactivity, and potential in synthesis of this kind of lithiated intermediates.Throughout the chapter, the name amino-organolithiums is used to describe reactive intermediates lithiated at sp 3 -hybridized carbon atoms adjacent (α) to a nitrogen atom that could be included also in a ring. Amino-organolithiums can be generated mainly in three different ways: (i) deprotonation of a parent amine or its derivative; (ii) transmetallation by using an alkyllithium; and (iii) reductive cleavage of C-heteroatom bond (e.g., C-S). Each way has advantages and disadvantages and in some cases they complement each other (Scheme 7.1).Direct deprotonation is a widely used strategy to generate amino-organolithiums even in chiral form, while tin-lithium exchange reactions are preferred when direct deprotonations are difficult (high kinetic barrier) or regiochemical issues apply. Concerning the direct deprotonation of amines, this is not a simple task because the corresponding lithiated intermediates suffer from destabilizing interactions that make this reaction very difficult unless a ''stabilizing group'' (SG) is introduced either on the nitrogen atom or on the lithium-bearing carbon (Scheme 7.2).The SG (Scheme 7.2) has a pivotal role, either reducing the kinetic barrier in the hydrogen/lithium permutation or stabilizing the organolithium mesomerically or by coordination. For these reasons, often, amino-organolithiums are classified as stabilized or unstabilized. The chemistry of unstabilized amino-organolithiums has been so far less developed however, lithiation of simple tertiary amines could be accomplished by two main strategies: (i) by tin/lithium exchange reaction and (ii) by deprotonation of quaternary ammonium complexes (Scheme 7.3).

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Addition of a Chiral Copper Reagent Derived from Propargylic Oxazolidininone to Aldehydes

Abstract: [reaction: see text] The copper reagent arising from an optically pure propargylic oxazolidinone was found to react regio- and diastereoselectively with aldehydes, leading, in a one-pot procedure, to the anti homopropargylic amino alcohols derivatives in good yields.

Cited by 25 publications

References 19 publications

Allenamides: A Powerful and Versatile Building Block in Organic Synthesis

Allenamides: A Powerful and Versatile Building Block in Organic Synthesis

Preparation of anti-1,2-Disubstituted Homopropargylic Alcohols by Addition of Allenyl(cyano)cuprates to Aldehydes

Nitrogen‐Bearing Lithium Compounds in Modern Synthesis

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