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DOI: 10.1055/s-0034-1379708
Diels–Alder Reactions with the >C=P– Functionality of Annelated Azaphospholes
Publication History
Received: 29 August 2014
Accepted after revision: 10 November 2014
Publication Date:
20 January 2015 (online)
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Abstract
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.
1 Background and Introduction
2 Scope and Limitations
3 Synthetic Methods
3.1 [4+1] Cyclocondensation Method
3.2 1,5-Electrocyclization Method
4 Energetics of the Diels–Alder Reaction with the >C=P– Functionality
5 Diels–Alder Reactions of Annelated 1,3-Azaphospholes
5.1 Diels–Alder Reactions of 1,3-Azaphospholo[1,5-a]pyridines, i.e., 2-Phosphaindolizines
5.2 Theoretical Investigation of the Dienophilic Reactivity of the >C=P– Functionality in 2-Phosphaindolizines
5.3 Theoretical Investigation of the Catalytic Effect of AlCl3 on the Dienophilic Reactivity of >C=C< and >C=P– Functionalities in Indolizine and 2-Phosphaindolizine
5.4 Organo-aluminum Chloride Catalyzed Diels–Alder Reactions of 2-Phosphaindolizines
5.5 Diels–Alder Reaction of 1,3-Azaphospholo[5,1-b]benzothiazole
6 Diels–Alder Reactions of Diazaphospholes
6.1 Diels–Alder Reactions of 1,4,2-Diazaphospholo[4,5-a]pyridines
6.2 Diels–Alder Reactions of Thiazolo[3,2-d][1,4,2]diazaphospholes and their 5,6-Dihydro and Benzo Derivatives
7 Conclusions