Asymmetric Diels–Alder reaction with &gt;C=P– functionality of the 2-phosphaindolizine-η<sup>1</sup>-P-aluminium(<i>O</i>-menthoxy) dichloride complex: experimental and theoretical results

Jangid, Rajendra K.; Sogani, N. C.; Gupta, Neelima; Bansal, R. K.; Hopffgarten, Moritz von; Frenking, Gernot

doi:10.3762/bjoc.9.40

Cited by 25 publications

(14 citation statements)

References 50 publications

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“…In accordance with the theoretical results, DA reaction of 2-phosphaindolizines ( 47 ) could be accomplished with complete diastereoselectivity, as indicated by 31 P NMR, with a single product being formed in each case ( Scheme 13 ) [ 40 ].…”

Section: Reactions Responsesupporting

confidence: 74%

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Synergy between Experimental and Theoretical Results of Some Reactions of Annelated 1,3-Azaphospholes

Bansal

Kour

2018

Molecules

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Computational calculations have been used successfully to explain the reactivity of the >C=P- functionality in pyrido-annelated 1,3-azaphospholes. Theoretical investigation at the Density Functional Theory (DFT) level shows that the lone pair of the bridgehead nitrogen atoms is involved in extended conjugation, due to which electron density increases considerably in the five-membered azaphosphole ring. The electron density in the azaphosphole is further enhanced by the presence of an ester group at the 3-position making the >C=P- functionality electron-rich. Thus, 1,3-azaphospholo[5,1-a]pyridine, i.e., 2-phosphaindolizine having ester group at the 3-position only does not undergo Diels-Alder (DA) reaction with an electron rich diene, such as 2,3-dimethyl-1,3-butadiene (DMB). However, an ester group at 1-position acts as electron-sink, due to which transfer of the electron density to the >C=P- moiety is checked and DA reaction occurs across the >C=P- functionality. The coordination of the Lewis acid to the carbonyl group at the 3-position raises the activation barrier, while it is lowered remarkably when it is coordinated to the P atom. Furthermore, the attack of 1,3-butadiene on the Si face of the P-coordinated (o-menthoxy)aluminum dichloride complex is a lower activation energy path. Fukui functions could be used to explain relative reactivities of indolizine and 2-phosphaindolizine towards electrophilic substitution reactions.

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Section: Reactions Responsesupporting

confidence: 74%

“…The successful results described above motivated us to investigate asymmetric DA reaction across the >C=P- moiety of 2-phosphaindolizines by using a chiral organoaluminium catalyst, namely, o-menthoxyaluminium dichloride [ 40 ].…”

Section: Reactions Responsementioning

confidence: 99%

Synergy between Experimental and Theoretical Results of Some Reactions of Annelated 1,3-Azaphospholes

Bansal

Kour

2018

Molecules

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“…This can be understood in terms of the weaker allylic CH bond (in propene) compared with common sp 3 CH bonds (in propane), 78.4 vs. 100.1 kcal mol −1 10. The discovery of InCl 2 + as the real catalyst is helpful for understanding the present cycloisomerization of 1,6‐enynes and other In(III),11a–c Al(III)6d and Bi(III)11d catalyzed reactions as well.…”

Section: Methodsmentioning

confidence: 99%

Control of Charge Transport in the Perovskite CH₃NH₃PbI₃ Thin Film

Shi

Wei

et al. 2015

ChemPhysChem

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Carrier density and transport properties in the CH3 NH3 PbI3 thin film have been investigated. It is found that the carrier density, the depletion field, and the charge collection and transport properties in the CH3 NH3 PbI3 absorber film can be controlled effectively by different concentrations of reactants. That is, the carrier properties and the self-doping characteristics in CH3 NH3 PbI3 films are strongly influenced by the reaction thermodynamic and kinetic processes. Furthermore, by employing mixed solvents with ethanol and isopropanol to deposit the CH3 NH3 PbI3 film, the charge collection and transport efficiencies are improved significantly, thereby yielding an overall enhanced cell performance.

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“…We subsequently accomplished the DA reaction of a 2-phosphaindolizine-η 1 -P-aluminum(O-menthoxy)dichloride complex with DMB in which the [2+4]cycloadducts were obtained with complete diastereoselectivity (Scheme 10). 31 Computational calculations revealed that the O-menthoxy moiety blocked the Re face of the >C=Pfunctionality directing the diene to attack from the Si face exclusively. 31…”

Section: Organo-aluminum Chloride Catalyzed Diels-alder Reactions Of 2-phosphaindolizinesmentioning

confidence: 99%

“…31 Computational calculations revealed that the O-menthoxy moiety blocked the Re face of the >C=Pfunctionality directing the diene to attack from the Si face exclusively. 31…”

Section: Organo-aluminum Chloride Catalyzed Diels-alder Reactions Of 2-phosphaindolizinesmentioning

confidence: 99%

Diels–Alder Reactions with the >C=P– Functionality of Annelated Azaphospholes

Bansal

Kour

2015

Synlett

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The >C=P-functionality in annelated azaphospholes acts as a dienophile and undergoes Diels-Alder reactions with dienes. 1,3-Bis(alkoxycarbonyl)-2-phosphaindolizines react with dienes even in the absence of a catalyst; however, in the presence of an oxidizing agent such as sulfur or selenium, the reaction is much faster. 3-Alkoxycarbonyl-2-phosphaindolizines with an electron-withdrawing group exclusively at position 3 undergo the Diels-Alder reaction only in the presence of a Lewis acid. Density functional theory calculations reveal strong hyperconjugative interactions between the nitrogen lone pair and the >C=P-functionality of the 3-alkoxycarbonyl-2-phosphaindolizine, making it electron-rich. However, in 1,3-bis(alkoxycarbonyl)-2-phosphaindolizines, the ester group at the position 1 acts as a sink for the lone pair of electrons of nitrogen leaving the >C=P-functionality sufficiently electron-deficient to undergo the Diels-Alder reaction.

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Asymmetric Diels–Alder reaction with >C=P– functionality of the 2-phosphaindolizine-η¹-P-aluminium(O-menthoxy) dichloride complex: experimental and theoretical results

Cited by 25 publications

References 50 publications

Synergy between Experimental and Theoretical Results of Some Reactions of Annelated 1,3-Azaphospholes

Synergy between Experimental and Theoretical Results of Some Reactions of Annelated 1,3-Azaphospholes

Control of Charge Transport in the Perovskite CH₃NH₃PbI₃ Thin Film

Diels–Alder Reactions with the >C=P– Functionality of Annelated Azaphospholes

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Asymmetric Diels–Alder reaction with >C=P– functionality of the 2-phosphaindolizine-η1-P-aluminium(O-menthoxy) dichloride complex: experimental and theoretical results

Cited by 25 publications

References 50 publications

Synergy between Experimental and Theoretical Results of Some Reactions of Annelated 1,3-Azaphospholes

Synergy between Experimental and Theoretical Results of Some Reactions of Annelated 1,3-Azaphospholes

Control of Charge Transport in the Perovskite CH3NH3PbI3 Thin Film

Diels–Alder Reactions with the >C=P– Functionality of Annelated Azaphospholes

Contact Info

Product

Resources

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Asymmetric Diels–Alder reaction with >C=P– functionality of the 2-phosphaindolizine-η¹-P-aluminium(O-menthoxy) dichloride complex: experimental and theoretical results

Control of Charge Transport in the Perovskite CH₃NH₃PbI₃ Thin Film