Linear‐Selective Allylation of Aldehydes with Simple Alkenes Mediated by Quadruple Hybrid Catalysis

Irie, Yu; Chen, Hongyu; Fuse, Hiroyuki; Mitsunuma, Harunobu; Kanai, Motomu

doi:10.1002/adsc.202200704

Cited by 6 publications

(5 citation statements)

References 79 publications

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“…This enantioselective methodology was the formation of linear products adding, as discussed in allylation section, Ni(BF4)2 as a Lewis acid. 53 It is worth to mention this methodology was really an advance in making chromium photoredox reactions suitable to be applied to natural product bearing polyketide structure. However, even in this case the simple allyl moiety was absent.…”

Section: Enatioselective Chromium Mediated Photoredox Reactionsmentioning

confidence: 99%

“…as HAT catalyst, and a catalytic amount of chromium complex in the presence of a Lewis acid (Scheme 4 ). 53 As briefly discussed in the example from the Glorius group, 49 a sulfur-centered radical (RS • ) is generated through single-electron oxidation of TPI by a photoexcited acridinium catalyst. The TPI • radical can form an allyl radical by atom hydrogen abstraction and the allyl radical is intercepted by the Cr(II) complex.…”

Section: Chromium Nucleophilic Organometallic Reagentsmentioning

confidence: 99%

“…89 This enantioselective methodology was also applied to the formation of linear products adding, as discussed Section 3.1, Ni(BF 4 ) 2 as a Lewis acid. 53…”

Section: Short Review Synthesismentioning

confidence: 99%

“…In 2022/2023, the Shi group reported the formation of a reactive allylcobalt by photoredox catalysis under the framework of a radical-to-polar crossover (Scheme 24). 116,117 They investigated the possibility of using the redox neutral system employed by the Glorius group 23 and Kanai, Mitsunuma, and co-workers 53 based on the formation of the allyl radical by oxidation of a C=C and deprotonation. Since the reduction potential of the cobalt complexes are lower compared to chromium, this limits the selection of suitable photoredox complexes for the reaction.…”

Section: Allylation Reactionsmentioning

confidence: 99%

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Developing Organometallic Nucleophilic Reagents Via Photoredox Catalysis

et al. 2023

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The addition of organometallic reagents to the carbonyl group represents a key transformation, both in Academia and industry. Most of these transformations rely in a mechanism in which accessible and reactive halides are transformed into the corresponding nucleophilic organometallic reactive compounds through a redox mechanism, using a metal (Cr, Mg, In, etc.) in low oxidation state, by electron transfer. With the advent of photoredox catalysis, the formation of radicals, through oxidation or reduction of suitable and tailored organic precursors, was merged with transition metal catalysis. By radical to polar crossover (RRPCO), a radical metal is combined with an organic radical to produce, via radical-radical trapping, a polar nucleophilic organometallic reagent. Using dual photoredox catalysis (metallaphotoredox catalysis), a reactive organometallic reagent could be prepared, avoiding the use of metals in low oxidation state. Herein, in addition to the description of the results obtained by our group and others’ contributions at the connection between carbonyl addition and radical-based photochemistry, we provide a core guiding for further synthetic developments. We anticipate that extending the photoredox dual strategy beyond the Barbier’s reactions described here, taming less-activated carbonyls, studying other important electrophiles, will realize important breakthroughs soon.

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Section: Enatioselective Chromium Mediated Photoredox Reactionsmentioning

confidence: 99%

Section: Chromium Nucleophilic Organometallic Reagentsmentioning

confidence: 99%

“…89 This enantioselective methodology was also applied to the formation of linear products adding, as discussed Section 3.1, Ni(BF 4 ) 2 as a Lewis acid. 53…”

Section: Short Review Synthesismentioning

confidence: 99%

Section: Allylation Reactionsmentioning

confidence: 99%

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Developing Organometallic Nucleophilic Reagents Via Photoredox Catalysis

et al. 2023

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“…Sparse examples are limited to two-component reactions of either alkanes or alkenes with aldehydes. Specifically, Kanai and Mitsunuma reported an elegant hybrid catalysis system, which combines an acridinium photoredox catalyst (Mes-Acr + ), a sophisticated thiophosphoric imide (TPI) HAT catalyst, and a chromium catalyst with or without a nickel catalyst and enables the reaction of unactivated alkenes and aldehydes through a HAT mechanistic pathway (Scheme a) . In addition, photoinduced, a tetrabutylammonium decatungstate (TBADT)/stoichiometric chromium reaction system and a catalytic system of CuCl 2 and CrCl 2 through the LMCT-HAT process can be applied for the coupling of alkanes and aldehydes (Scheme b).…”

mentioning

confidence: 99%

1,3-Butadiene Dicarbofunctionalization Enabled by the Dual Role of Diaryl Ketone in Photo-HAT/Chromium Catalysis

Hu,

Song,

Zeng

et al. 2024

Org. Lett.

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We report a three-component Nozaki–Hiyama–Kishi type reaction of 1,3-dioxolane, 1,3-butadienes, and aldehydes to access masked aldehyde-incorporated homoallylic alcohols, facilitated by photo-hydrogen atom transfer (HAT)/chromium dual catalysis. The diaryl ketone serves dual roles both in the HAT process and in facilitating the turnover of the chromium catalyst. A range of functional groups are tolerated owing to the mild conditions. Both aromatic and aliphatic aldehydes are suitable substrates for coupling with several 1,3-butadienes and 1,3-dioxolane.

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Chromium in Visible‐Light Photocatalysis: Unique Reactivity, Mechanisms and Future Directions

Shen,

2024

Eur J Org Chem

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Visible‐light photocatalysis has emerged as a prominent research area in modern organic synthesis and environmental science. As an important transition metal, chromium has garnered widespread attention in the field of visible‐light photocatalysis in recent years, primarily manifested in the following aspects: a) the unique photochemical properties of chromium(III) complexes endow them with longer excited‐state lifetimes and higher reactivities; b) by harnessing visible light to induce single‐electron transfer or hydrogen atom transfer to generate radicals, which subsequently form alkyl‐chromium(III) intermediates with chromium(II) ligands, these intermediates can selectively attack electron‐deficient carbonyl compounds, enabling the construction of target products; c) following metals like cerium, copper, iron, nickel, cobalt, titanium, and bismuth, the ligand‐to‐metal charge transfer (LMCT) reaction pathways in chromium photocatalysis have also been extensively investigated.This review will provide a comprehensive summary of recent research on chromium‐mediated photocatalytic reactions, offering an in‐depth exploration of their unique reactivity, mechanisms, and future directions.

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Linear‐Selective Allylation of Aldehydes with Simple Alkenes Mediated by Quadruple Hybrid Catalysis

Cited by 6 publications

References 79 publications

Developing Organometallic Nucleophilic Reagents Via Photoredox Catalysis

Developing Organometallic Nucleophilic Reagents Via Photoredox Catalysis

1,3-Butadiene Dicarbofunctionalization Enabled by the Dual Role of Diaryl Ketone in Photo-HAT/Chromium Catalysis

Chromium in Visible‐Light Photocatalysis: Unique Reactivity, Mechanisms and Future Directions

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