Corrigendum: Pyridylidene‐Mediated Dihydrogen Activation Coupled with Catalytic Imine Reduction

Auth, Johanna; Padevet, Jaroslav; Mauleón, Pablo; Pfaltz, Andreas

doi:10.1002/anie.201706608

Cited by 2 publications

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“…The nature of this intermediate is uncertain and will be the focus of subsequent studies, but the observed 1 H signals are inconsistent with a 2‐pyridinylidene ( 15RR’ ) that has traditionally been proposed as the intermediate in the formation of BPYs [12] . Such species have been generated from pyridinium ions and trapped by metals, [48] sulfur, [48,49] and H 2 , [50,51] and we therefore suspect they are still involved in the formation of 3RR’ , despite being undetected.…”

Section: Resultsmentioning

confidence: 86%

Bis(Iminophosphorano)‐Substituted Pyridinium Ions and their Corresponding Bispyridinylidene Organic Electron Donors

Frenette

Arsenault

Walker

et al. 2021

Chemistry A European J

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Optimized synthetic procedures for pyridinium ions featuring iminophosphorano (−N=PR3; R=Ph, Cy) π‐donor substituents in the 2‐ and 4‐ positions are described. Crystallographic and theoretical studies reveal that the strongly donating substituents severely polarize the π‐electrons of the pyridyl ring at the expense of aromaticity. Moreover, the pyridinium ions are readily deprotonated to generate powerful bispyridinylidene (BPY) organic electron donors. Electrochemical studies show exceptionally low redox potentials for the two‐electron BPY/BPY2+ couples, ranging from −1.71 V vs the saturated calomel electrode for 3PhPh (with four Ph3P=N− groups) to −1.85 V for 3CyCy (with four Cy3P=N− groups). These new compounds represent the most reducing neutral organic electron donors (OEDs) currently known. Some preliminary reductions involving 3CyCy showed enhanced capability owing to its low redox potential, such as the thermally activated reduction of an aryl chloride, but purification challenges were often encountered.

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Section: Resultsmentioning

confidence: 86%

Bis(Iminophosphorano)‐Substituted Pyridinium Ions and their Corresponding Bispyridinylidene Organic Electron Donors

Frenette

Arsenault

Walker

et al. 2021

Chemistry A European J

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“…During the course of our work on H 2 activation with pyridinium salts and base,, we studied the reduction of imine 1 (Scheme ), which took place upon treatment with a pyridinium salt, LiN(SiMe 3 ) 2 , and H 2 . We found that the reaction did not proceed, as initially assumed, through hydride transfer from a dihydropyridine generated from the pyridinium salt by deprotonation and subsequent addition of H 2 .…”

Section: Methodsmentioning

confidence: 99%

H₂ Activation by Non‐Transition‐Metal Systems: Hydrogenation of Aldimines and Ketimines with LiN(SiMe₃)₂

Elliott

Martí

Mauleón

et al. 2019

Chemistry A European J

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In recent years, H2 activation at non‐transition‐metal centers has met with increasing attention. Here, a system in which H2 is activated and transferred to aldimines and ketimines using substoichiometric amounts of lithium bis(trimethylsilyl)amide is reported. Notably, the reaction tolerates the presence of acidic protons in the α‐position. Mechanistic investigations indicated that the reaction proceeds via a lithium hydride intermediate as the actual reductant.

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Corrigendum: Pyridylidene‐Mediated Dihydrogen Activation Coupled with Catalytic Imine Reduction

Cited by 2 publications

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Bis(Iminophosphorano)‐Substituted Pyridinium Ions and their Corresponding Bispyridinylidene Organic Electron Donors

Bis(Iminophosphorano)‐Substituted Pyridinium Ions and their Corresponding Bispyridinylidene Organic Electron Donors

H₂ Activation by Non‐Transition‐Metal Systems: Hydrogenation of Aldimines and Ketimines with LiN(SiMe₃)₂

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Corrigendum: Pyridylidene‐Mediated Dihydrogen Activation Coupled with Catalytic Imine Reduction

Cited by 2 publications

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Bis(Iminophosphorano)‐Substituted Pyridinium Ions and their Corresponding Bispyridinylidene Organic Electron Donors

Bis(Iminophosphorano)‐Substituted Pyridinium Ions and their Corresponding Bispyridinylidene Organic Electron Donors

H2 Activation by Non‐Transition‐Metal Systems: Hydrogenation of Aldimines and Ketimines with LiN(SiMe3)2

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H₂ Activation by Non‐Transition‐Metal Systems: Hydrogenation of Aldimines and Ketimines with LiN(SiMe₃)₂