An Organometallic Umpolung Approach for Iron‐Mediated Propargylic C–H Etherification DOI Creative Commons
Yue Xia, Jin Zhu,

Austin C. Durham

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 27, 2024

Abstract Propargylic ethers serve as useful intermediates for the synthesis of a variety complex targets. However, propargylic substitution prefunctionalized alkyne starting materials remains dominant method propargyl ethers, while direct etherification simple alkynes via C−H functionalization largely underreported. Herein, we report an organometallic umpolung approach iron‐mediated etherification. A telescopic protocol deprotonation followed by mild oxidative coupling with alcohols enabled use or functionalized expedient excellent functional group compatibility, chemoselectivity and regioselectivity.

Language: Английский

Facile Access to Hindered Ethers via Photoinduced O–H Bond Insertions DOI Creative Commons
Yu Zhang, Xinyu Han,

Dong Li

et al.

ACS Central Science, Journal Year: 2025, Volume and Issue: unknown

Published: April 23, 2025

The synthesis of the hindered and polyfluorinated dialkyl ethers poses challenges owing to bulkiness tertiary alcohols low nucleophilicity alcohols. Additionally, associated competitive side reactions always provide poor reactivities. Although certain strategies, such as electrocatalytic decarboxylation hydroalkoxylation, have been explored, a straightforward method for obtaining with structural diversity remains elusive. In this study, we exploited photoinduced approach that involves in situ formation singlet carbenes followed by O-H insertions access congested or Moreover, other nucleophiles phenols, H2O, thiols, silanols, tributyltin hydride, etc., are also tolerable obtain valuable products. gram-scale marketed drugs modification complex molecules demonstrate practicality approach. detailed mechanistic studies elucidated key intermediates reaction mechanism, which were distinct from traditional metal-carbenoid insertions.

Language: Английский

Citations

0
Facile Access to Hindered Ethers via Photoinduced O-H Bond Insertions DOI Creative Commons
Yu Zhang, Xinyu Han,

Dong Li

et al.

Published: July 15, 2024

The synthesis of the hindered and polyfluorinated dialkyl ethers poses challenges owing to bulkiness tertiary alcohols low nucleophilicity alcohols. Additionally, associated competitive side reactions always provide poor reactivities. Although certain strategies, such as electrocatalytic decarboxylation hydroalkoxylation, have been explored, a straightforward method for obtaining with structural diversity remains elusive. In this study, we proposed photoinduced approach that involved in-situ formation singlet carbenes followed by O-H insertions access ethers. This successfully converted diverse congested into their corresponding challenging Moreover, other nucleophiles phenols, H2O, thiols, silanols, tributyltin hydride etc. were tolerable obtain valuable products. gram-scale marketed drugs modification complex molecules demonstrated practicality approach. detailed mechanistic studies elucidated key intermediates reaction mechanisms.

Language: Английский

Citations

1
An Organometallic Umpolung Approach for Iron‐Mediated Propargylic C–H Etherification DOI Creative Commons
Yue Xia, Jin Zhu,

Austin C. Durham

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 27, 2024

Abstract Propargylic ethers serve as useful intermediates for the synthesis of a variety complex targets. However, propargylic substitution prefunctionalized alkyne starting materials remains dominant method propargyl ethers, while direct etherification simple alkynes via C−H functionalization largely underreported. Herein, we report an organometallic umpolung approach iron‐mediated etherification. A telescopic protocol deprotonation followed by mild oxidative coupling with alcohols enabled use or functionalized expedient excellent functional group compatibility, chemoselectivity and regioselectivity.

Language: Английский

Citations

1
Diastereoselective Homocoupling of Benzylic C(sp3)–H Bonds Enabled by Halogen Transfer DOI
Xirong Liu, Xin An, Xue Zhao

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(43), P. 9257 - 9262

Published: Oct. 18, 2024

A transition-metal- and harsh-oxidant-free strategy for diastereoselective homocoupling of benzylic α-boryl carbanions has been developed. Central to this methodology is the ability halogen transfer reagent seamlessly integrate halogenation substitution within a compatible process. Additionally, also applicable diarylmethanes alkylheteroarenes. Substrates bearing oxidatively sensitive functional groups were well-tolerated. Preliminary studies suggest that hydrogen bond between two boryl contributes high diastereoselectivities.

Language: Английский

Citations

0
An Organometallic Umpolung Approach for Iron‐Mediated Propargylic C–H Etherification DOI Creative Commons
Yue Xia, Jin Zhu,

Austin C. Durham

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 27, 2024

Abstract Propargylic ethers serve as useful intermediates for the synthesis of a variety complex targets. However, propargylic substitution prefunctionalized alkyne starting materials remains dominant method propargyl ethers, while direct etherification simple alkynes via C−H functionalization largely underreported. Herein, we report an organometallic umpolung approach iron‐mediated etherification. A telescopic protocol deprotonation followed by mild oxidative coupling with alcohols enabled use or functionalized expedient excellent functional group compatibility, chemoselectivity and regioselectivity.

Language: Английский

Citations

0