DFT Study on the Mechanism of Phosphine-Catalyzed Ring-Opening Reaction of Cyclopropyl Ketone DOI
Xiaohan Yu, Yang Wang

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

In the present study, mechanism, origin of chemoselectivity, and substituent effects phosphine-catalyzed ring-opening reaction cyclopropyl ketone have been investigated using DFT method. Multiple pathways, including formation hydrofluorenone, Cloke-Wilson product, cyclopenta-fused were studied compared. The computational results show that pathway for hydrofluorenone is most favorable one, which involves four processes: nucleophilic substitution to open three-membered ring, an intramolecular Michael addition enolate intermediate, [1,5]-proton transfer give ylide, Wittig deliver final product. For disclosing structural analysis local reactivity index performed. Moreover, also considered QTAIM analysis. current study would provide useful insights understanding chemoselective reactions.

Language: Английский

Lewis Acid-Enabled Chemodivergent Cycloadditions of Donor–Acceptor Cyclopropanes with Indoline-2-Thiones DOI

Chen-Ying Zhai,

Bing Zhao, Xuelong Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 20, 2025

Lewis acid-enabled reactions of donor-acceptor cyclopropanes (DACs) with indoline-2-thiones are reported. The reaction exhibits tunable annulation depending on the acid and substituent at N1 indoline-2-thiones. With AlCl3 as 1-isopropylindoline-2-thiones reactants, a direct ring opening DACs, followed by intramolecular nucleophilic addition/dehydration takes place leading to formation dihydro-2H-thiepino[2,3-b]indoles in moderate good yields. Using Yb(OTf)3 promoter 1-unsubstituted (3 + 2) cycloaddition DACs accompanied sulfur rearrangement give 3-indolyl-4,5-dihydrothiophenes In addition, synthetic transformation 3-indolyl-4,5-dihydrothiophene sulfone indole-based axially chiral scaffolds further extends utility structural complexity.

Language: Английский

Citations

1
DFT Study on the Mechanism of Phosphine-Catalyzed Ring-Opening Reaction of Cyclopropyl Ketone DOI
Xiaohan Yu, Yang Wang

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

In the present study, mechanism, origin of chemoselectivity, and substituent effects phosphine-catalyzed ring-opening reaction cyclopropyl ketone have been investigated using DFT method. Multiple pathways, including formation hydrofluorenone, Cloke-Wilson product, cyclopenta-fused were studied compared. The computational results show that pathway for hydrofluorenone is most favorable one, which involves four processes: nucleophilic substitution to open three-membered ring, an intramolecular Michael addition enolate intermediate, [1,5]-proton transfer give ylide, Wittig deliver final product. For disclosing structural analysis local reactivity index performed. Moreover, also considered QTAIM analysis. current study would provide useful insights understanding chemoselective reactions.

Language: Английский

Citations

1