Synthetic applications of NHPs: from the hydride pathway to a radical mechanism

Zhang, Yushan; Huan, Zhen; Yang, Jin‐Dong; Cheng, Jiang

doi:10.1039/d2cc04844b

Chem. Commun.

2022

DOI: 10.1039/d2cc04844b

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Synthetic applications of NHPs: from the hydride pathway to a radical mechanism

Yushan Zhang

Zhen Huan

Jin‐Dong Yang

et al.

Abstract: The unique heterocyclic skeletons of N-heterocyclic phosphines (NHPs) endow them with excellent hydridic reactivity, which have enabled a great array of catalytic hydrogenations of unsaturated substrates in the past decades....

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Cited by 5 publications

References 56 publications

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Reductive Asymmetric Aza‐Mislow‐Evans Rearrangement by 1,3,2‐Diazaphospholene Catalysis**

Zhang

Cramer

2023

Angewandte Chemie

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1,3,2‐diazaphospholene hydrides (DAP−H) enable smooth conjugate reduction of polarized double bonds. The transiently formed phosphorus‐enolate provides a potential platform for reductive α‐functionalizations. In this respect, asymmetric C‐heteroatom bond forming processes are synthetically appealing but remain elusive. We report a 1,3,2‐diazaphospholene‐catalyzed three‐step cascade reaction of N‐sulfinyl acrylamides comprised of conjugate reduction, [2,3]‐sigmatropic aza‐Mislow‐Evans rearrangement and subsequent S−O bond cleavage. The obtained enantio‐enriched α‐hydroxy amides are formed in good yields and excellent enantiospecificity. The stereo‐defined P‐bound N,O‐ketene aminal ensures an excellent transfer of chirality from the sulfur stereocenter to α‐carbon. The transformation operates under mild conditions at ambient temperature. Moreover, DAP−H is a competent reductant for the cleavage of formed sulfenate ester, eliminating the extra step in traditional Mislow‐Evans processes.

show abstract

Reductive Asymmetric Aza‐Mislow‐Evans Rearrangement by 1,3,2‐Diazaphospholene Catalysis**

Zhang

Cramer

2023

Angewandte Chemie

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(3+2) Annulation of 4‐Acetoxy Allenoate with Aldimine Enabled by AgF‐Assisted P(III)/P(V) Catalysis

Qian,

Zhou,

Peng

et al. 2023

Angewandte Chemie

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A phosphine‐catalyzed (3+2) annulation of 4‐acetoxy allenoate and aldimine with the assistance of AgF is described. The success of this reaction hinges on the metathesis between the enolate‐phosphonium zwitterion and AgF, leading to a key intermediate comprising of silver enolate and a fluorophosphorane P(V)‐moiety. The former is able to undergo a Mannich reaction with aldimine, whereas the latter initiates a cascade sequence of AcO‐elimination/aza‐addition, thus furnishing the P(III)/P(V) catalysis. By taking advantage of the silver enolate, a preliminary attempt at an asymmetric variant was conducted with the combination of an achiral phosphine catalyst and a chiral bis(oxazolinyl)pyridine ligand (PyBox), giving moderate enantioselectivity.

show abstract

Reductive Asymmetric Aza‐Mislow‐Evans Rearrangement by 1,3,2‐Diazaphospholene Catalysis**

Zhang

Cramer

2023

Angew Chem Int Ed

View full text Add to dashboard Cite

1,3,2-diazaphospholene hydrides (DAPÀ H) enable smooth conjugate reduction of polarized double bonds. The transiently formed phosphorus-enolate provides a potential platform for reductive α-functionalizations. In this respect, asymmetric C-heteroatom bond forming processes are synthetically appealing but remain elusive. We report a 1,3,2-diazaphospholene-catalyzed three-step cascade reaction of N-sulfinyl acrylamides comprised of conjugate reduction, [2,3]-sigmatropic aza-Mislow-Evans rearrangement and subsequent SÀ O bond cleavage. The obtained enantio-enriched α-hydroxy amides are formed in good yields and excellent enantiospecificity. The stereo-defined P-bound N,Oketene aminal ensures an excellent transfer of chirality from the sulfur stereocenter to α-carbon. The transformation operates under mild conditions at ambient temperature. Moreover, DAPÀ H is a competent reductant for the cleavage of formed sulfenate ester, eliminating the extra step in traditional Mislow-Evans processes.

show abstract

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Synthetic applications of NHPs: from the hydride pathway to a radical mechanism

Abstract: The unique heterocyclic skeletons of N-heterocyclic phosphines (NHPs) endow them with excellent hydridic reactivity, which have enabled a great array of catalytic hydrogenations of unsaturated substrates in the past decades....

Cited by 5 publications

References 56 publications

Reductive Asymmetric Aza‐Mislow‐Evans Rearrangement by 1,3,2‐Diazaphospholene Catalysis**

Reductive Asymmetric Aza‐Mislow‐Evans Rearrangement by 1,3,2‐Diazaphospholene Catalysis**

(3+2) Annulation of 4‐Acetoxy Allenoate with Aldimine Enabled by AgF‐Assisted P(III)/P(V) Catalysis

Reductive Asymmetric Aza‐Mislow‐Evans Rearrangement by 1,3,2‐Diazaphospholene Catalysis**

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