Density Functional Theory Study of the Mechanisms of Iron-Catalyzed Intramolecular C–H Amination [1,2]-Shift Tandem Reactions of Aryl Azides

Ren, Qinghua; Shen, Xin; Wan, Jinyu; Fang, Jianhui

doi:10.1021/acs.organomet.5b00087

Cited by 15 publications

(8 citation statements)

References 57 publications

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“…The observation on the retention of the cyclopropyl group, on the other hand, suggests that the C-H bond amination step in this FeBr 2 -catalzyed reactions might be distinct from the classical H-abstraction/radical rebound mechanism. Ren and coworkers performed DFT calculations on the mechanism of this FeBr 2 -catalzyed reaction, [71] and found that a concerted *2σ+2π+-addition between iron imido moiety and a C-H bond to form iron amido hydrido species is energetically favored over the classical radical type C-H amination mechanism (Scheme 10).…”

Section: C-h Bond Amination Reactions Catalyzed By Non-heme-type Ironmentioning

confidence: 99%

Recent Advances in Iron‐Catalyzed C—H Bond Amination via Iron Imido Intermediate

Wang

Deng

2018

Chin. J. Chem.

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Transition‐metal‐catalyzed C—H bond amination reaction is an attractive method for the synthesis of amines. Fueled by the growing interests in the development of economical and eco‐friendly catalysts for organic transformations, there are great recent efforts on developing iron‐catalyzed C—H bond amination reactions using organic azides, sulfonyl azides, and iminoiodanes as nitrene source. This review summarizes the progress achieved in the field since 2011. The reaction scope, the synthetic utility of the catalytic reaction, and the current mechanistic understandings of the C—H bond amination reactions catalyzed by hemoproteins, iron porphyrins and phthalocyanines, non‐heme‐type iron complexes, as well as metal‐organic‐ framework‐supported iron complexes are introduced and discussed.

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Section: C-h Bond Amination Reactions Catalyzed By Non-heme-type Ironmentioning

confidence: 99%

Recent Advances in Iron‐Catalyzed C—H Bond Amination via Iron Imido Intermediate

Wang

Deng

2018

Chin. J. Chem.

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“…The hydroxylation of unactivated methylene catalyzed by P450 PikC that is engineered from pikromycin natural biosynthetic pathway has been examined . However, computational studies on P450 with an iron nitrenoid cofactor that can functionalize C–H bonds are lacking, although there were studies on iron nitrenoid-mediated C–H activations without P450. − In this work, the mechanism of P450-catalyzed C–H amination was studied by QM/MM calculations. On the basis of this study, the regio- and stereoselectivity of this reaction can be explained.…”

Section: Introductionmentioning

confidence: 99%

Computational Study of Engineered Cytochrome P450-Catalyzed C–H Amination: The Origin of the Regio- and Stereoselectivity

Burnell

Boyd

2017

J. Phys. Chem. B

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Cytochrome P450 enzymes were recently engineered to catalyze the C-H amination reaction of aryl sulfonyl azides with excellent regio- and stereoselectivity (Arnold and co-workers J. Am. Chem. Soc. 2014 , 136 , 15505 ). The mechanism of this reaction was studied by quantum mechanical (QM)/molecular mechanical (MM) calculations in this work. The C-H activation is found to be a stepwise process consisting of hydrogen abstraction (H-abstraction) of the reactive C-H bond by an iron nitrenoid cofactor to produce the biradical intermediate and subsequent radical rebinding to form the final product. The rate of rotation of the carbon radical center was estimated to be much faster than that of radical rebinding, which implies that the H-abstraction does not determine the stereoselectivity. For mutant A, the H-abstraction step has a barrier of 16.7 kcal/mol, which is 3.0 kcal/mol higher than that of the following radical rebinding step. The H-abstraction step determines the regioselectivity, but the radical rebinding step determines the stereoselectivity. Barriers of these two steps are 16.1 and 27.5 kcal/mol, respectively, for mutant B. It is different from mutant A in that the radical rebinding step has the higher barrier and determines both the regio- and stereoselectivity. The initial distances between the hydrogens of reactive C-H bonds and the iron nitrenoid were found to not correlate with their reactivities. The calculated barriers are qualitatively consistent with the experimentally observed regio- and stereoselectivity with the exception of the stereoselectivity of mutant B. The lower barriers of mutant A presumably come from the stabilization effect of the H-bond between G265 and the sulfone O. This H-bond does not exist in mutant B. The conformation of the protein backbone, with the exception of the active site, does not change much (RMSD < 0.05) along the reaction pathway.

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“…According to the Bredt’s rule, the intermediate V with a bridgehead double bond is highly strained and thus will go through rearrangement quickly. Through a multistep rearrangement, , the intermediate V transformed to the final product 3 .…”

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confidence: 99%

“…6 No formation of their corresponding cyclopenta [c] will go through rearrangement quickly. Through a multistep rearrangement, 11,12 the intermediate V transformed to the final product 3.…”

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confidence: 99%

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Formation of Cyclopenta[c]pyridine Derivatives from 2,5-Disubstituted Pyrroles and 1,4-Dibromo-1,3-butadienes via Pyrrole-Ring One-Carbon Expansion

Yin

Wei

et al. 2016

Org. Lett.

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Reactions between 1,4-dibromo-1,3-butadienes and 2,5-disubstituted pyrroles afforded cyclopenta[c]pyridine derivatives in high yield, catalyzed by palladium and a cyclopentadiene-phosphine ligand (L1). Insertion of one terminal carbon of the butadienyl skeleton into one C═C double bond in the pyrrole ring resulted in ring expansion, along with a 1,2-shift of an alkyl or an aryl substituent on the butadienes.

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Density Functional Theory Study of the Mechanisms of Iron-Catalyzed Intramolecular C–H Amination [1,2]-Shift Tandem Reactions of Aryl Azides

Cited by 15 publications

References 57 publications

Recent Advances in Iron‐Catalyzed C—H Bond Amination via Iron Imido Intermediate

Recent Advances in Iron‐Catalyzed C—H Bond Amination via Iron Imido Intermediate

Computational Study of Engineered Cytochrome P450-Catalyzed C–H Amination: The Origin of the Regio- and Stereoselectivity

Formation of Cyclopenta[c]pyridine Derivatives from 2,5-Disubstituted Pyrroles and 1,4-Dibromo-1,3-butadienes via Pyrrole-Ring One-Carbon Expansion

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