Cyclic Iodonium Ylide Unlocked Pd-Catalyzed α-Acyloxylation of Cyclic 1,3-Dicarbonyls with Carboxylic Acids DOI
Huanping Xie,

Borong Su,

H. -L. Cui

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 10, 2024

To date, a general approach for the direct α-acyloxylation of cyclic 1,3-dicarbonyls remains challenging. Herein, we report Pd-catalyzed 1,3-dicarbonyl-derived hypervalent iodine compounds with highly abundant carboxylic acids. Our utilizes commercially available Pd(OAc)

Language: Английский

Exploring the role of halogen bonding in iodonium ylides: insights into unexpected reactivity and reaction control DOI Creative Commons
Carlee A. Montgomery, Graham K. Murphy

Beilstein Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 19, P. 1171 - 1190

Published: Aug. 7, 2023

Halogen bonding is commonly found with iodine-containing molecules, and it arises when Lewis bases interact iodine's σ-holes. σ-holes have been encountered in numerous monovalent hypervalent compounds, 2022 were computationally confirmed quantified the iodonium ylide subset of iodine compounds. In light this new discovery, article provides an overview reactions ylides which halogen has invoked. Herein, we summarize key discoveries mechanistic proposals from early literature that invoked bonding-type mechanisms, as well recent reports between basic nucleophiles specifically The discussed herein are organized to enable reader build understanding how might impact yield chemoselectivity outcomes ylides. Areas focus include nucleophile σ-hole selectivity, structural modifications intramolecular (e.g., ortho-effect) can improve stability or solubility, alter reaction outcomes.

Language: Английский

Citations

11
Does a halogen bond require positive potential on the acid and negative potential on the base? DOI
Steve Scheiner

Physical Chemistry Chemical Physics, Journal Year: 2023, Volume and Issue: 25(10), P. 7184 - 7194

Published: Jan. 1, 2023

It is usually expected that formation of a halogen bond (XB) requires region positive electrostatic potential associated with σ or π-hole on the Lewis acid will interact negative base, either lone pair π-bond region. Quantum calculations model systems suggest this not to be necessary. The placement electron-withdrawing substituents base can reverse sign in its positive, and nonetheless engage XB σ-hole acid. scenario also possible certain circumstances, as negatively charged form base. Despite these classical Coulombic repulsions, overall interaction attractive XBs, albeit only weakly so. strengths bonds are surprisingly insensitive changes partner molecule. For example, even wide range depth approaching yields minimal change strength potential.

Language: Английский

Citations

8
Efficient Carbene Transfer Reactivity Mediated by Fe(II) Complexes Supported by Bulky Alkoxides DOI Creative Commons

Lakshani Wathsala Kulathungage,

Sudheer S. Kurup,

Edison A. Browne

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(55), P. 7033 - 7036

Published: Jan. 1, 2024

Herein we describe the stoichiometric and catalytic carbene-transfer reactivity of iron(II) alkoxide complexes with iodonium ylide precursors. Treatment PhIC(CO

Language: Английский

Citations

1
Cyclic Iodonium Ylide Unlocked Pd-Catalyzed α-Acyloxylation of Cyclic 1,3-Dicarbonyls with Carboxylic Acids DOI
Huanping Xie,

Borong Su,

H. -L. Cui

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 10, 2024

To date, a general approach for the direct α-acyloxylation of cyclic 1,3-dicarbonyls remains challenging. Herein, we report Pd-catalyzed 1,3-dicarbonyl-derived hypervalent iodine compounds with highly abundant carboxylic acids. Our utilizes commercially available Pd(OAc)

Language: Английский

Citations

1