tert-Butanesulfinimines: structure, synthesis and synthetic applications

Ferreira, Franck; Botuha, Candice; Chemla, Fabrice; Pérez‐Luna, Alejandro

doi:10.1039/b809772k

Cited by 308 publications

(85 citation statements)

References 124 publications

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“…As far as we know,t his is the first successful example of ap arallel kinetic resolution in the Rauhut-Currier reaction. Further applications of Xiao-Phos variants as organocatalysts or chiral ligands for transition metals in asymmetric reactions and as ap recursor to other chiral phosphines [19] are currently underway in our laboratory and will be reported in due course.…”

Section: Methodsmentioning

confidence: 98%

Design, Synthesis, and Application of a Chiral Sulfinamide Phosphine Catalyst for the Enantioselective Intramolecular Rauhut–Currier Reaction

Zhou

et al. 2015

Angewandte Chemie

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An ovel class of chiral sulfinamide phosphine catalysts (Xiao-Phos) are reported, which can be easily prepared from inexpensive commercially available starting materials.The Xiao-Phos catalysts showed good performance in enantioselective intramolecular Rauhut-Currier reactions, generating a-methylene-g-butyrolactones in high yields with up to 99 %e eu nder mild conditions.M oreover,k inetic resolution and parallel kinetic resolution were also observed with the use of two different substituted racemic precursors.Over the past decade,a symmetric nucleophilic catalysis with chiral phosphines has emerged as apowerful approach to structurally diverse and synthetically valuable optically active organic building blocks.[1] Among the many types of chiral phosphines,c hiral b-aminephosphines represent one of the most attractive and have been utilized as nucleophilic catalysts [2] or chiral ligands [3] in ab road spectrum of useful organic transformations.Compared to the intensive attention focused on the utility of chiral b-aminephosphines in organic synthesis,only ahandful of methods have been reported so far for their synthesis.A mong these,t he approach from readily available natural or unnatural chiral amino acids is the most attractive.[4] Despite the fact that much progress has been made in the construction of chiral phosphine catalysts,t he development/design of highly efficient new types of chiral phosphines,e specially from inexpensive,c ommercially available chiral resources,r emains ac onsiderable challenge.Recently,o ur group developed an ew type of chiral sulfinamide phosphine (Ming-Phos ligands), which could be easily prepared in good yields from inexpensive commercially available chiral tert-butylsulfinamide in two steps.G ratifyingly,M ing-Phos ligands have shown good performance in asymmetric transition-metal catalysis and the sulfinamide plays asecond role in stereoselectivity control.[5] With aseries of chiral Ming-Phos ligands in hand and as ap art of our program for developing chiral-phosphine-catalyzed enantioselctive transformations, [6] we wished to expand the applications of Ming-Phos variants from transition-metal catalysis to nucleophilic phosphine catalysis.I nt his context, recent elegant work by Sasai and co-workers [7] attracted our attention. They successfully accomplished ac hiral-phosphine-catalyzed enantioselective intramolecular RauhutCurrier (RC) reaction, [8] efficiently furnishing synthetically valuable a-methylene-g-butyrolactones.[9] However, the performance of the Ming-Phos variants was disappointing;i n most cases,the reaction did not give high conversions because of the low nucleophilic catalyst activity.W et hen envisaged that anew type of chiral sulfinamide phosphines,called XiaoPhos,should have better nucleophilic activity than the MingPhos variants.With two stereocenters,anH-bonding site,and tunable side chains,the Xiao-Phos series may be applicable to asymmetric nucleophilic catalysis for organic transformations such as RC reactions (Figure 1). Herein, we report o...

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Section: Methodsmentioning

confidence: 98%

Design, Synthesis, and Application of a Chiral Sulfinamide Phosphine Catalyst for the Enantioselective Intramolecular Rauhut–Currier Reaction

Zhou

et al. 2015

Angewandte Chemie

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“…The use of chiral optically pure amines as the chiral auxiliary for achieving the highly diastereoselective Strecker reaction has evolved into a relatively general and robust approach for accessing various enantiomerically pure α-amino acids. [12][13][14][15][16][17][18] The first example of a diastereoselective Strecker reaction assisted by a chiral auxiliary on the amine component was reported by Harada, who used (S)-1-phenylethylamine as the chiral auxiliary to obtain chiral (S)-α-amino acids after acid hydrolysis of the nitrile and cleavage and recovery of the N-alkyl group. …”

Section: Diastereoselective Strecker Reactionsmentioning

confidence: 99%

Recent advances on asymmetric Strecker reactions

Cai¹,

Xie²

2014

Arkivoc

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The Strecker reaction is one of the most attractive methods for the synthesis of α-amino acids and other bioactive compounds including natural products. The asymmetric Strecker reaction represents a simple and efficient method for the synthesis of optically pure α-amino acid derivatives, nucleic acids, various nitrogen and sulfur containing heterocycles and pharmaceuticals. Over the past several decades, considerable effort has been devoted towards the development of asymmetric Strecker reactions. This review provides an overview of recent asymmetric Strecker reactions, from diastereoselective reactions and catalytic enantioselective reactions including chiral catalytic metal systems and chiral organocatalytic systems.

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“…Indeed, the pioneering works of Davis and Ellman on the synthesis and reactivity of N-sulfinyl imines have given the synthetic community a readily available and robust precursor of optically active amine compounds. [8][9][10][11][12][13][14][15][16] Due to this rarity of radical species-mediated methods as well as our ongoing interest in radical reactions, [17][18][19] we sought to improve the efficiency and substrate scope of our initial report on radical addition of ethers and acetals to enantiopure N-p-toluenesulfinyl aldimines. 20) In this previous report, an in-house dimethylzinc-air radical initiator was used to generate carbon-centered a-alkoxyalkyl radicals from ethers and acetals.…”

Section: Notesmentioning

confidence: 99%

Stereoselective Radical Addition of an Acetal to Sterically Tuned Enantiomerically Pure N-Sulfinyl Imines

Akindele

Yamada

Sejima

et al. 2010

CHEMICAL & PHARMACEUTICAL BULLETIN

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NotesGiven the ubiquitous nature of the C-N stereogenic center, efficient synthetic methods continue to be developed for its installation in both simple and complex chemical structures.1-3) These methods could be broadly classified into reactions mediated by ionic or radical species. Majority of these methods are mediated by ionic species, requiring highly basic reagents which limit the substrate scope of these approaches, albeit the products are obtained in high yield and enantioselectivity. On the other hand, methods involving radical species 4,5) are relatively under explored despite the potential of this approach to deliver much more structurally varied products using milder reagents.To date, the lack of a catalytic asymmetric radical addition method to N-sulfonyl imines 6,7) has made the use of chiral Nsulfinyl imines as radical acceptors, for creating predictable stereodefined C-N stereogenic centers in sulfonamides, an appealing alternative synthetic strategy. Indeed, the pioneering works of Davis and Ellman on the synthesis and reactivity of N-sulfinyl imines have given the synthetic community a readily available and robust precursor of optically active amine compounds. [8][9][10][11][12][13][14][15][16] Due to this rarity of radical species-mediated methods as well as our ongoing interest in radical reactions, [17][18][19] we sought to improve the efficiency and substrate scope of our initial report on radical addition of ethers and acetals to enantiopure N-p-toluenesulfinyl aldimines. 20) In this previous report, an in-house dimethylzinc-air radical initiator was used to generate carbon-centered a-alkoxyalkyl radicals from ethers and acetals. Subsequent nucleophilic addition of the radicals to the enantiopure N-sulfinyl imines followed by oxidation afforded the sulfonamide adducts in enantiomerically enriched forms. It is noteworthy that boron trifluoride diethyl etherate was essential for faster reaction rate while a sterically hindered acetal was crucial to good stereocontrol (Chart 1).Subsequent investigations have led to improved levels of stereocontrol. Herein, we detail our new findings along with a computational rationale for the improved levels of stereocontrol. Results and DiscussionAs we previously reported, 20) the reaction of (S)-Nbenzylidene-4-toluenesulfinamide (1a) with acetal 2 21) proceeded smoothly in the presence of trifluoroborane diethyl etherate using dimethylzinc-air to give a crude mixture including sulfinamide products 6a with a 9 : 1 diastereomeric ratio along with a trace amount of sulfonamide product 3a (ca. 1%). Subsequent oxidation of the crude products with m-chloroperbenzoic acid (m-CPBA) provided 3a with 80% ee in 92% yield (Table 1, entry 1). The enantiomeric ratio of 3a was the same as the diastereomeric ratio of 6a in the crude mixture, showing that no racemization took place during the m-CPBA oxidation.We reasoned that by substituting a bulkier group for the ptolyl group on the sulfur stereogenic center would presumably lead to higher levels of stereocontrol. In fac...

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tert-Butanesulfinimines: structure, synthesis and synthetic applications

Cited by 308 publications

References 124 publications

Design, Synthesis, and Application of a Chiral Sulfinamide Phosphine Catalyst for the Enantioselective Intramolecular Rauhut–Currier Reaction

Design, Synthesis, and Application of a Chiral Sulfinamide Phosphine Catalyst for the Enantioselective Intramolecular Rauhut–Currier Reaction

Recent advances on asymmetric Strecker reactions

Stereoselective Radical Addition of an Acetal to Sterically Tuned Enantiomerically Pure N-Sulfinyl Imines

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