Thiophosphoramide‐Based Cooperative Catalysts for Brønsted Acid Promoted Ionic Diels–Alder Reactions

Borovika, Alina; Tang, Pui‐in; Klapman, Seth; Nagorny, Pavel

doi:10.1002/ange.201307133

Angewandte Chemie

2013

DOI: 10.1002/ange.201307133

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Thiophosphoramide‐Based Cooperative Catalysts for Brønsted Acid Promoted Ionic Diels–Alder Reactions

Alina Borovika¹,

Pui‐in Tang²,

Seth Klapman³

et al.

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Cited by 23 publications

(1 citation statement)

References 39 publications

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“…Recently, we became interested in exploring the unique reactivities of the unsaturated oxocarbenium 2, which can be formed by protonation of the unsaturated acetals 1 (Figure 1). [7] Ionic [2+4] cycloadditions are perhaps the most well-known transformations associated with the intermediacy of 2. [3] However, less common reactions such as aza-Michael reactions, proceeding through 2', could be envisioned once the analogy between 2 and the species 3 and 4 is drawn.…”

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Enantioselective Synthesis of Piperidines through the Formation of Chiral Mixed Phosphoric Acid Acetals: Experimental and Theoretical Studies

et al. 2014

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An enantioselective intramolecular chiral phosphoric acid-catalyzed cyclization of unsaturated acetals has been utilized for the synthesis of functionalized chiral piperidines. The chiral enol ether products of these cyclizations undergo subsequent in situ enantioenrichment through acetalization of the minor enantiomer. A new computational reaction exploration method was utilized to elucidate the mechanism and stereoselectivity of this transformation. Rather than confirming the originally postulated cyclization proceeding directly through a vinyl oxocarbenium ion, simulations identified an alternative two-step mechanism involving the formation of a mixed chiral phosphate acetal, which undergoes a concerted, asynchronous S(N)2'-like displacement to yield the product with stereoselectivity in agreement with experimental observations.

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confidence: 99%

Enantioselective Synthesis of Piperidines through the Formation of Chiral Mixed Phosphoric Acid Acetals: Experimental and Theoretical Studies

et al. 2014

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Heterocycle Synthesis Based on Allylic Alcohol Transposition Using Traceless Trapping Groups

Xie

Floreancig

2014

Angewandte Chemie

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Allylic alcohols undergo transposition reactions in the presence of Re2O7 whereby the equilibrium can be dictated by trapping one isomer with a pendent electrophile. Additional ionization can occur when the trapping group is an aldehyde or ketone, thus leading to cyclic oxocarbenium ion formation. Terminating the process through bimolecular nucleophilic addition into the intermediate provides a versatile method for the synthesis of diverse oxygen‐containing heterocycles. Understanding the relative rates of the steps in the sequence leads to the design of reactions which create multiple stereocenters with good to excellent levels of control.

show abstract

Enantioselective Synthesis of Piperidines through the Formation of Chiral Mixed Phosphoric Acid Acetals: Experimental and Theoretical Studies

et al. 2014

Self Cite

View full text Add to dashboard Cite

An enantioselective intramolecular chiral phosphoric acid‐catalyzed cyclization of unsaturated acetals has been utilized for the synthesis of functionalized chiral piperidines. The chiral enol ether products of these cyclizations undergo subsequent in situ enantioenrichment through acetalization of the minor enantiomer. A new computational reaction exploration method was utilized to elucidate the mechanism and stereoselectivity of this transformation. Rather than confirming the originally postulated cyclization proceeding directly through a vinyl oxocarbenium ion, simulations identified an alternative two‐step mechanism involving the formation of a mixed chiral phosphate acetal, which undergoes a concerted, asynchronous SN2′‐like displacement to yield the product with stereoselectivity in agreement with experimental observations.

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Thiophosphoramide‐Based Cooperative Catalysts for Brønsted Acid Promoted Ionic Diels–Alder Reactions

Cited by 23 publications

References 39 publications

Enantioselective Synthesis of Piperidines through the Formation of Chiral Mixed Phosphoric Acid Acetals: Experimental and Theoretical Studies

Enantioselective Synthesis of Piperidines through the Formation of Chiral Mixed Phosphoric Acid Acetals: Experimental and Theoretical Studies

Heterocycle Synthesis Based on Allylic Alcohol Transposition Using Traceless Trapping Groups

Enantioselective Synthesis of Piperidines through the Formation of Chiral Mixed Phosphoric Acid Acetals: Experimental and Theoretical Studies

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