Selective Reduction of Amino Allenephosphonates: Preparation of α‐Amino Vinylphosphonates

Adler, Pauline; Gomes, Filipe; Fadel, Antoine; Rabasso, Nicolas

doi:10.1002/ejoc.201300904

Cited by 19 publications

(25 citation statements)

References 36 publications

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“…1c ). Before studies in the regioselective semireduction of allenes have shown that the less substituted π -bond is typically reduced to afford the achiral internal alkene 16 – 18 . Existing methods that reduce the more substituted π -bond are limited to monosubstituted and symmetrical allenes, which give rise to achiral terminal alkenes 19 , 20 .…”

Section: Introductionmentioning

confidence: 99%

Enantioselective semireduction of allenes

Chen

Dong

2017

Nat Commun

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Rh-hydride catalysis solves a synthetic challenge by affording the enantioselective reduction of allenes, thereby yielding access to motifs commonly used in medicinal chemistry. A designer Josiphos ligand promotes the generation of chiral benzylic isomers, when combined with a Hantzsch ester as the reductant. This semireduction proceeds chemoselectively in the presence of other functional groups, which are typically reduced using conventional hydrogenations. Isotopic labelling studies support a mechanism where the hydride is delivered to the branched position of a Rh-allyl intermediate.

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Section: Introductionmentioning

confidence: 99%

Enantioselective semireduction of allenes

Chen

Dong

2017

Nat Commun

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“…In 2012, Rabasso published a [2,3]-sigmatropic rearrangement of N -alkynyl amides [118]. The following year, 2013, during their investigations into the selective reduction of amino-allenephosphonates, Rabasso expanded the scope of their [2,3]-sigmatropic rearrangement to include N -alkynyl indole (Scheme 75) [119].…”

Section: Reactions Of N-alkynyl Azolesmentioning

confidence: 99%

Preparation and Utility of N-Alkynyl Azoles in Synthesis

Reinus

Kerwin

2019

Molecules

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Heteroatom-substituted alkynes have attracted a significant amount of interest in the synthetic community due to the polarized nature of these alkynes and their utility in a wide range of reactions. One specific class of heteroatom-substituted alkynes combines this utility with the presence of an azole moiety. These N-alkynyl azoles have been known for nearly 50 years, but recently there has been a tremendous increase in the number of reports detailing the synthesis and utility of this class of compound. While much of the chemistry of N-alkynyl azoles mirrors that of the more extensively studied N-alkynyl amides (ynamides), there are notable exceptions. In addition, as azoles are extremely common in natural products and pharmaceuticals, these N-alkynyl azoles have high potential for accessing biologically important compounds. In this review, the literature reports of N-alkynyl azole synthesis, reactions, and uses have been assembled. Collectively, these reports demonstrate the growth in this area and the promise of exploiting N-alkynyl azoles in synthesis.

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“…With the emergence of the α-amino vinylphosphonate as an important building block for the preparation of biologically active molecules [15], the research on developing heterogeneous catalysts for selective hydrogenation of α-amino allenephosphonates to α-amino vinylphosphonates has drawn interest [16]. The most efficient heterogeneous catalyst for 1,2-hydrogenation was determined to be the Pd/C (10 wt.%) in the presence of quinoline.…”

Section: Introductionmentioning

confidence: 99%

Alkanethiolate-Capped Palladium Nanoparticles for Regio- and Stereoselective Hydrogenation of Allenes

Chen

Shon

2018

Catalysts

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Colloidal Pd nanoparticles capped with octanethiolate ligands have previously shown an excellent selectivity toward the mono-hydrogenation of both isolated and conjugated dienes to internal alkenes. This paper reports an efficient stereoselective mono-hydrogenation of cumulated dienes (allenes) to either Z or E olefinic isomers, depending on the substitution pattern around C=C bonds. Kinetic studies indicate that the reaction progresses through the hydrogenation of less hindered C=C bonds to produce internal Z olefinic isomers. In the cases of di-substitued olefinic products, this initial hydrogenation step is followed by the subsequent isomerization of Z to E isomers. In contrast, the slow isomerization of Z to E isomers for tri-substituted olefinic products results in the preservation of Z stereochemistry. The high selectivity of Pd nanoparticles averting an additional hydrogenation is steered from the controlled electronic and geometric properties of the Pd surface, which are the result of thiolate-induced partial poisoning and surface crowding, respectively. The high activity of colloidal Pd nanoparticle catalysts allows the reactions to be completed at room temperature and atmospheric pressure.

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Selective Reduction of Amino Allenephosphonates: Preparation of α‐Amino Vinylphosphonates

Cited by 19 publications

References 36 publications

Enantioselective semireduction of allenes

Enantioselective semireduction of allenes

Preparation and Utility of N-Alkynyl Azoles in Synthesis

Alkanethiolate-Capped Palladium Nanoparticles for Regio- and Stereoselective Hydrogenation of Allenes

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