Hydrofunctionalization of Propadiene – New Life for a Previously Unwanted Product

Sieger, Simon V.; Lubins, Ilja; Breit, Bernhard

doi:10.1021/acscatal.2c03105

“…41 The title compound was prepared according to the general procedure and purified by flash (2-(Allylsulfonyl)ethyl)benzene (3ag). 42 The title compound was prepared according to the general procedure and purified by flash column chromatography on silica gel to give a yellow oil, 39.0 mg, 62% yield. Eluent: (petroleum ether/ethyl acetate = 5/1).…”

Section: -(Allylsulfonyl)-3-methylbenzo[d]oxazol-2(3h)-one (3xmentioning

confidence: 99%

Photoredox-Catalyzed Radical–Radical Cross-Coupling of Sulfonyl Chlorides with Trifluoroborate Salts

Liu

¹

,

He

²

,

Guan

³

2023

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Sulfones are widely found in natural products and drug molecules. Here, we disclose a strategy for direct synthesis of sulfone compounds with diverse structures by visible-lightcatalyzed radical−radical cross-coupling of sulfonyl chlorides and trifluoroborate salts. Allyl, benzyl, vinyl, and aryl trifluoroborates can be successfully cross-coupled with (hetero)aryl and alkyl sulfonyl chlorides, respectively. This strategy features redox neutrality, good substrate generality, simple operation, and benign reaction conditions.

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“…Recently, considerable progress has been achieved in transition metal‐catalyzed asymmetric hydrofunctionalizations [22, 23] of conjugated dienes [24–48] . We thus envisioned that the long‐time unsolved umpolung nucleophilic 1,5‐addition might be realized if suitably defined palladium hydride catalysis [49–60] was identified (Scheme 1b). However, classical hydrofunctionalizations of conjugated dienes are limited to the use of inert aryl and alkyl units as substituents [22–48] .…”

Section: Introductionmentioning

confidence: 99%

Umpolung Asymmetric 1,5‐Conjugate Addition via Palladium Hydride Catalysis

Wang

¹

,

Xiao

²

,

Wang

³

et al. 2022

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Electronically matched nucleophilic 1,6-conjugate addition has been well studied and widely applied in synthetic areas. In contrast, nucleophilic 1,5-conjugate addition represents an electronically forbidden process and is considered unfeasible. Here, we describe modular protocols for 1,5-conjugate addition reactions via palladium hydride catalysis. Both palladium and synergistic Pd/organocatalyst systems are developed to catalyze 1,5conjugate reaction, followed by inter-or intramolecular [3+2] cyclization. A migratory 1,5-addition protocol is established to corroborate the feasibility of this umpolung concept. The 1,5-addition products are conveniently transformed into a series of privileged enantioenriched motifs, including polysubstituted tetrahydrofuran, dihydrofuran, cyclopropane, cyclobutane, azetidine, oxetane, thietane, spirocycle and bridged rings. Preliminary mechanistic studies corroborate the involvement of palladium hydride catalysis.

show abstract

“…Recently, considerable progress has been achieved in transition metal‐catalyzed asymmetric hydrofunctionalizations [22, 23] of conjugated dienes [24–48] . We thus envisioned that the long‐time unsolved umpolung nucleophilic 1,5‐addition might be realized if suitably defined palladium hydride catalysis [49–60] was identified (Scheme 1b). However, classical hydrofunctionalizations of conjugated dienes are limited to the use of inert aryl and alkyl units as substituents [22–48] .…”

Section: Introductionmentioning

confidence: 99%

Umpolung Asymmetric 1,5‐Conjugate Addition via Palladium Hydride Catalysis

Wang

¹

,

Xiao

²

,

Wang

³

et al. 2022

Angewandte Chemie

1

0

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Electronically matched nucleophilic 1,6-conjugate addition has been well studied and widely applied in synthetic areas. In contrast, nucleophilic 1,5-conjugate addition represents an electronically forbidden process and is considered unfeasible. Here, we describe modular protocols for 1,5-conjugate addition reactions via palladium hydride catalysis. Both palladium and synergistic Pd/organocatalyst systems are developed to catalyze 1,5conjugate reaction, followed by inter-or intramolecular [3+2] cyclization. A migratory 1,5-addition protocol is established to corroborate the feasibility of this umpolung concept. The 1,5-addition products are conveniently transformed into a series of privileged enantioenriched motifs, including polysubstituted tetrahydrofuran, dihydrofuran, cyclopropane, cyclobutane, azetidine, oxetane, thietane, spirocycle and bridged rings. Preliminary mechanistic studies corroborate the involvement of palladium hydride catalysis.

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Hydrofunctionalization of Propadiene – New Life for a Previously Unwanted Product

Cited by 15 publications

References 51 publications

Photoredox-Catalyzed Radical–Radical Cross-Coupling of Sulfonyl Chlorides with Trifluoroborate Salts

Photoredox-Catalyzed Radical–Radical Cross-Coupling of Sulfonyl Chlorides with Trifluoroborate Salts

Umpolung Asymmetric 1,5‐Conjugate Addition via Palladium Hydride Catalysis

Umpolung Asymmetric 1,5‐Conjugate Addition via Palladium Hydride Catalysis

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