Benzoyldiisopropylchlorosilane: a visible light photocleavable alcohol protecting group

Lind, Florian; Markelov, Kirill; Studer, Armido

doi:10.1039/d3sc04975b

Cited by 4 publications

(1 citation statement)

References 29 publications

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“…However, the relatively high bond dissociation energy (BDE = 83.9 kcal/mol) of the benzyl C–H bond poses a challenge to hydrogen abstraction under mild conditions. Photocatalysis, possessing redox properties, offers a possibility for the selective activation of C–H bonds that traditional methods hardly achieve. − Based on our previous research, uranyl photocatalysis features a ligand-to-metal charge transfer (LMCT) excitation mode with high oxidation potential ( E ° = +2.6 V versus standard hydrogen electrode), especially the ability for hydrogen atom transfer (HAT). Herein, a safe and practical uranyl-photocatalytic debenzylation strategy was established with moisture- and oxidation-sensitive compatibility.…”

Section: Introductionmentioning

confidence: 99%

Deprotection of Benzyl-Derived Groups via Uranyl-Photocatalysis

Meng,

Ji,

Jiang

2024

Organometallics

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To circumvent the hazards associated with flammable/explosive hydrogen and address substrate compatibility issues in reductive systems, we developed a mild method for benzyl deprotection facilitated by uranium under visible light irradiation at ambient conditions. The uranium-oxo species, as a metal-oxo-type photosensitizer, demonstrates compatibility with moisture, enabling benzyl C−H activation through ligand-to-metal charge transfer (LMCT) excitation. Subsequent capture of the benzyl radical by atmospheric oxygen induces oxidation at the benzylic position. Removal of the semiacetal occurs, resulting in C−O bond cleavage under acidic conditions. This methodology, featuring mild conditions and operational convenience, is compatible with moisture and oxygen. It presents a complementary strategy for benzyl deprotection for the synthesis of pharmaceuticals and organic materials.

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Section: Introductionmentioning

confidence: 99%

Deprotection of Benzyl-Derived Groups via Uranyl-Photocatalysis

Meng,

Ji,

Jiang

2024

Organometallics

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Organophotocatalyzed C−Si Bond Fragmentation Using Silyl Ethers as Radical Precursors

Luguera Ruiz,

Benazzi,

Tucci

et al. 2024

Adv Synth Catal

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In this work, silyl ethers of phenols and alcohols have been successfully prepared and tested as neutral carbon (silicon) centered radical precursors. The organocophotocatalyzed oxidation (by the Fukuzumi catalyst) of these ethers caused the cleavage of a C‐Si (or a Si‐Si) bond for the release of the desired radical to be used for the forging of C(sp3)‐C(sp3) (or C(sp3)‐Si) bonds via a Giese reaction.

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Versatile Synthesis of α‐Oxygen Organoboron Compounds via Photo‐Induced Siloxycarbene^†

Lu,

Zhao,

Cao

et al. 2024

Chin. J. Chem.

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Comprehensive SummaryA novel method for synthesizing α‐oxygen organoboron compounds has been developed through acylsilane‐based carbene insertion reactions into C—B bonds. As coupling partners, readily available organoboron compounds (alkenyl, allyl, and allenyl B(pin)) were employed. Based on the substrates, pure insertion into C—B bonds or insertion followed by a siloxy group rearrangement process (from carbon to boron) would occur, delivering the α‐oxygen organoboron compounds with great diversities. Control experiments demonstrated that the electronic effect of the substituents mainly controlled the rearrangement process. Besides, no matter which isomer of substrate (Z or E) was used, the reaction with β‐aryl‐substituted alkenyl B(pin) affords both isomers of products (Z and E, separable through column chromatography). Trapping experiments indicated the triplet energy transfer process was involved.

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Benzoyldiisopropylchlorosilane: a visible light photocleavable alcohol protecting group

Abstract: Silyl chlorides are highly valuable and popular reagents for the protection of alcohols. In this edge article we introduce a photocleavable alcohol protecting group on the basis of acyl silanes....

Cited by 4 publications

References 29 publications

Deprotection of Benzyl-Derived Groups via Uranyl-Photocatalysis

Deprotection of Benzyl-Derived Groups via Uranyl-Photocatalysis

Organophotocatalyzed C−Si Bond Fragmentation Using Silyl Ethers as Radical Precursors

Versatile Synthesis of α‐Oxygen Organoboron Compounds via Photo‐Induced Siloxycarbene^†

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Benzoyldiisopropylchlorosilane: a visible light photocleavable alcohol protecting group

Abstract: Silyl chlorides are highly valuable and popular reagents for the protection of alcohols. In this edge article we introduce a photocleavable alcohol protecting group on the basis of acyl silanes....

Cited by 4 publications

References 29 publications

Deprotection of Benzyl-Derived Groups via Uranyl-Photocatalysis

Deprotection of Benzyl-Derived Groups via Uranyl-Photocatalysis

Organophotocatalyzed C−Si Bond Fragmentation Using Silyl Ethers as Radical Precursors

Versatile Synthesis of α‐Oxygen Organoboron Compounds via Photo‐Induced Siloxycarbene†

Contact Info

Product

Resources

About

Versatile Synthesis of α‐Oxygen Organoboron Compounds via Photo‐Induced Siloxycarbene^†