A DFT mechanistic study on [4 + 3] cycloaddition reactions of oxyallyl cations and five-membered cyclopentadiene derivatives

Amoah, Anthony; Tia, Richard; Adei, Evans

doi:10.1016/j.tet.2020.131422

Cited by 4 publications

(3 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Concerted 1,3-dipolar cycloadditions are often studied with computational modeling. [5,7,[11][12][13][54][55][56][57][58] The cycloadditions to nitrile oxides of substituted alkenes and alkynes are no exception. [11,13,59,60] Most noticeable computational studies address regioselectivity of 1,3-dipolar cycloadditions.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Negligible Substituent Effect as Key to Synthetic Versatility: a Computational‐Experimental Study of Vinyl Ethers Addition to Nitrile Oxides

et al. 2022

View full text Add to dashboard Cite

A tangible substituent effect may be perceived as a good feature in developing an organic reaction. This work demonstrates that, on the contrary, a zero-slope Hammet plot should be sought. The synthesis of isoxazoles by consecutive cycloaddition of nitrile oxides to vinyl ethers and alcohols elimination was studied computationally and experimentally. We performed a Hammett study in silico to demonstrate a negligible substituent effect (i. e., broad substrate scope) in the addition of benzyl vinyl ether to nitrile oxides. The modeling was performed at the ωB97X-V/def2-TZVP//PBE0-D4/def2-TZVP + SMD(benzene) level of theory within the RIJCOSX approximation. The experimental evaluation validated the computational model. A versatile methodology for synthesizing substituted isoxazolines and isoxazoles was proposed as the main result. We present this work as a successful example of how quantum chemical modeling can re-boost the classic Hammett approach to the optimization and design of organic synthetic methodologies. We anticipate further Hammett studies in silico, considering the current trend for data-driven chemical research.

show abstract

Section: Introductionmentioning

confidence: 99%

“…Concerted 1,3‐dipolar cycloadditions are often studied with computational modeling [5,7,11–13,54–58] . The cycloadditions to nitrile oxides of substituted alkenes and alkynes are no exception [11,13,59,60] .…”

Section: Introductionmentioning

confidence: 99%

Negligible Substituent Effect as Key to Synthetic Versatility: a Computational‐Experimental Study of Vinyl Ethers Addition to Nitrile Oxides

et al. 2022

View full text Add to dashboard Cite

show abstract

“…Oxyallyls are versatile reactive intermediates and have been extensively used as electrophiles , and dipolarophiles − in various reactions. Their synthetic utility is amply demonstrated by the synthesis of natural products. − However, owing to the unique planar structure of oxyallyls for which there is no general means to discriminate between the two faces, catalytic asymmetric reactions involving oxyallyls remain largely unexplored.…”

mentioning

confidence: 99%

Catalytic Asymmetric (3 + 3) Cycloaddition of Oxyallyl Zwitterions with α-Diazomethylphosphonates

et al. 2021

View full text Add to dashboard Cite

The unique structure of oxyallyls represents a significant challenge for their catalytic asymmetric applications. Herein, an unprecedented chiral imidodiphosphoric acid-catalytic enantioselective (3 + 3) cycloaddition between oxyallyl zwitterions generated in situ from α-haloketones and α-diazomethylphosphonates was developed. Pharmaceutically interesting chiral pyridazine-4(1H)-ones were obtained in up to 98% yields with excellent stereoselectivities (up to 99% ee, > 99:1 dr).

show abstract

Addition Reactions: Cycloaddition

Dennis

2024

Organic Reaction Mechanisms 2020

View full text Add to dashboard Cite

A DFT mechanistic study on [4 + 3] cycloaddition reactions of oxyallyl cations and five-membered cyclopentadiene derivatives

Cited by 4 publications

References 26 publications

Negligible Substituent Effect as Key to Synthetic Versatility: a Computational‐Experimental Study of Vinyl Ethers Addition to Nitrile Oxides

Negligible Substituent Effect as Key to Synthetic Versatility: a Computational‐Experimental Study of Vinyl Ethers Addition to Nitrile Oxides

Catalytic Asymmetric (3 + 3) Cycloaddition of Oxyallyl Zwitterions with α-Diazomethylphosphonates

Addition Reactions: Cycloaddition

Contact Info

Product

Resources

About