Gold catalysed site-selective cross-coupling of tertiary α-silylamines with 1-iodoalkynes under UVA LED light

Yichao Zhao; James Theodore Merrett; Jianwen Jin; Li Juan Yu; Michelle Louise Coote; Philip Wai Hong Chan

doi:10.1039/d2qo01581a

Gold catalysed site-selective cross-coupling of tertiary α-silylamines with 1-iodoalkynes under UVA LED light

Yichao Zhao, James Theodore Merrett, Jianwen Jin, Li Juan Yu, Michelle Louise Coote, Philip Wai Hong Chan

Research output: Contribution to journal › Article › Research › peer-review

2 Citations (Scopus)

Abstract

A synthetic method that relies on [Au₂(μ-dppm)₂]Cl₂ (dppm = bis(diphenylphosphino)methane) and UVA LED (LED = light emitting diode) light (λ = 365 nm) to mediate the α-alkynylation of tertiary α-silylamines by 1-iodoalkynes is described. The site-selective desilylative C(sp³)-C(sp) bond formation protocol was demonstrated to exhibit excellent functional group tolerance as it was applicable to a broad range of coupling partners and a variety of bioactive molecules and natural products. Experimental and computational studies suggest the reaction mechanism follows an oxidative quench pathway that generates the two surmised radical species of the amine and alkyne substrates. It also implied the possible involvement of the dimeric metal complex in mediating the ensuing cross-coupling of the two radical species, which is unprecedented in photoredox gold(i,i) catalysis.

Original language	English
Pages (from-to)	759-766
Number of pages	8
Journal	Organic Chemistry Frontiers
Volume	10
Issue number	3
DOIs	https://doi.org/10.1039/d2qo01581a
Publication status	Published - 7 Feb 2023

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10.1039/d2qo01581a

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title = "Gold catalysed site-selective cross-coupling of tertiary α-silylamines with 1-iodoalkynes under UVA LED light",

abstract = "A synthetic method that relies on [Au2(μ-dppm)2]Cl2 (dppm = bis(diphenylphosphino)methane) and UVA LED (LED = light emitting diode) light (λ = 365 nm) to mediate the α-alkynylation of tertiary α-silylamines by 1-iodoalkynes is described. The site-selective desilylative C(sp3)-C(sp) bond formation protocol was demonstrated to exhibit excellent functional group tolerance as it was applicable to a broad range of coupling partners and a variety of bioactive molecules and natural products. Experimental and computational studies suggest the reaction mechanism follows an oxidative quench pathway that generates the two surmised radical species of the amine and alkyne substrates. It also implied the possible involvement of the dimeric metal complex in mediating the ensuing cross-coupling of the two radical species, which is unprecedented in photoredox gold(i,i) catalysis.",

author = "Yichao Zhao and Merrett, {James Theodore} and Jianwen Jin and Yu, {Li Juan} and Coote, {Michelle Louise} and Chan, {Philip Wai Hong}",

note = "Funding Information: This work was supported by a Discovery Project Grant (DP210103425) from the Australian Research Council and Scientific Research Starting Foundation of Jiyang College of Zhejiang A&F University Fund (04251700022). Publisher Copyright: {\textcopyright} 2023 The Royal Society of Chemistry.",

year = "2023",

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doi = "10.1039/d2qo01581a",

language = "English",

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journal = "Organic Chemistry Frontiers",

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T1 - Gold catalysed site-selective cross-coupling of tertiary α-silylamines with 1-iodoalkynes under UVA LED light

AU - Zhao, Yichao

AU - Merrett, James Theodore

AU - Jin, Jianwen

AU - Yu, Li Juan

AU - Coote, Michelle Louise

AU - Chan, Philip Wai Hong

N1 - Funding Information: This work was supported by a Discovery Project Grant (DP210103425) from the Australian Research Council and Scientific Research Starting Foundation of Jiyang College of Zhejiang A&F University Fund (04251700022). Publisher Copyright: © 2023 The Royal Society of Chemistry.

PY - 2023/2/7

Y1 - 2023/2/7

N2 - A synthetic method that relies on [Au2(μ-dppm)2]Cl2 (dppm = bis(diphenylphosphino)methane) and UVA LED (LED = light emitting diode) light (λ = 365 nm) to mediate the α-alkynylation of tertiary α-silylamines by 1-iodoalkynes is described. The site-selective desilylative C(sp3)-C(sp) bond formation protocol was demonstrated to exhibit excellent functional group tolerance as it was applicable to a broad range of coupling partners and a variety of bioactive molecules and natural products. Experimental and computational studies suggest the reaction mechanism follows an oxidative quench pathway that generates the two surmised radical species of the amine and alkyne substrates. It also implied the possible involvement of the dimeric metal complex in mediating the ensuing cross-coupling of the two radical species, which is unprecedented in photoredox gold(i,i) catalysis.

AB - A synthetic method that relies on [Au2(μ-dppm)2]Cl2 (dppm = bis(diphenylphosphino)methane) and UVA LED (LED = light emitting diode) light (λ = 365 nm) to mediate the α-alkynylation of tertiary α-silylamines by 1-iodoalkynes is described. The site-selective desilylative C(sp3)-C(sp) bond formation protocol was demonstrated to exhibit excellent functional group tolerance as it was applicable to a broad range of coupling partners and a variety of bioactive molecules and natural products. Experimental and computational studies suggest the reaction mechanism follows an oxidative quench pathway that generates the two surmised radical species of the amine and alkyne substrates. It also implied the possible involvement of the dimeric metal complex in mediating the ensuing cross-coupling of the two radical species, which is unprecedented in photoredox gold(i,i) catalysis.

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DO - 10.1039/d2qo01581a

M3 - Article

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SN - 2052-4129

VL - 10

SP - 759

EP - 766

JO - Organic Chemistry Frontiers

JF - Organic Chemistry Frontiers

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ER -

Gold catalysed site-selective cross-coupling of tertiary α-silylamines with 1-iodoalkynes under UVA LED light

Abstract

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New catalytic alkyne cyclisation strategies for complex molecule synthesis

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Gold catalysed site-selective cross-coupling of tertiary α-silylamines with 1-iodoalkynes under UVA LED light

Abstract

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New catalytic alkyne cyclisation strategies for complex molecule synthesis

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