Intramolecular Ring Expansion of 3-Silaazetidine with Alkynes Enabled by Pd-Catalyzed Si–C Bond Activation

Fan, Yu; Jing, Jun; Tong, Ruiqi; Tu, Xiaoyu; L, Gao; Wang, Wanshu; Song, Zhenlei

doi:10.1021/acs.orglett.2c03698

Cited by 5 publications

(2 citation statements)

References 49 publications

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“…Ring expansion reactions of small silacycles frequently are catalysed by transition metals, and a plethora of substitution patterns and ring sizes is accessible among which the expansion of siletanes with alkynes is probably the best investigated example [2,40–43] . To date, this work could be extended to asymmetric products [43–45] and Si−N heterocycles recently [46,47] . A notable exception is the non‐catalysed insertion of CO 2 into siletanes [48] .…”

Section: Introductionmentioning

confidence: 99%

“…[2,[40][41][42][43] To date, this work could be extended to asymmetric products [43][44][45] and SiÀ N heterocycles recently. [46,47] A notable exception is the non-catalysed insertion of CO 2 into siletanes. [48] Moreover, in the reactions of transient silylenes with alkynes, occasionally silole formation was observed, even though this is not a generally applicable way of preparing them.…”

Section: Introductionmentioning

confidence: 99%

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Strain‐Driven, Non‐Catalysed Ring Expansion of Silicon Heterocycles

Müller,

Hinz

2023

Chemistry A European J

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Silacycles are ubiquitous building blocks. Small silacycles can typically be expanded catalytically. We have prepared a silirane (1), silirene (2) and phosphasilirene (3) as well as a siletane (4) and a silolene (5) starting from the base‐free bromosilylene [(dtbpCbz)SiBr]. As these heterocycles were derived from a dicoordinated silylene, they are susceptible to reactions with an external base. The three‐membered silacycles readily undergo non‐catalysed ring expansion reactions with isonitriles yielding the related four‐membered silacycles. Surprisingly, the ring‐expanded derivatives of the silirane 1 undergo up to two further isomerisation reactions, first by enamine formation and then by another ring expansion. DFT computations were utilised to gauge the scope of this reactivity pattern. Three‐membered silacycles should essentially universally undergo a ring expansion with isonitriles, while for four‐membered silacycles, only very few instances are predicted to accommodate more challenging kinetic requirements of this ring expansion. Larger silacycles lack the ring strain energy required for this ring expansion reaction and are not expected to be expanded.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Strain‐Driven, Non‐Catalysed Ring Expansion of Silicon Heterocycles

Müller,

Hinz

2023

Chemistry A European J

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Rhodium-Catalyzed Hydrolytic Cleavage of the Silicon–Carbon Bond of Silacyclobutanes to Access Silanols

Zhu,

Fang

et al. 2023

Org. Lett.

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Controllable Si–C Bond Formation from Trihydrosilanes En Route to Synthesis of 1,4-Azasilinanes with Diverse Silyl Functionalities

Guo,

Liu,

Jing

et al. 2023

Org. Lett.

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A B(C6F5)3-catalyzed controllable inter/intra-/intermolecular Si–C bond formation process has been developed from trihydrosilane and dienamide with alkenes, anilines, or aryl iodides. A variety of 1,4-azasilinanes have been generated with diverse exo-cyclic heteroleptic disubstitutions on silicon, thereby expanding the range of silaazacyclic rings available for the discovery of silicon-containing drugs.

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Intramolecular Ring Expansion of 3-Silaazetidine with Alkynes Enabled by Pd-Catalyzed Si–C Bond Activation

Abstract: An intramolecular ring expansion of in situ formed 3-silaazetidine with internal alkynes has been developed via Pd-catalyzed Si–C bond activation. The reaction gives rise to 6,5- and 6,6-fused bicyclic 1,3-azasilines, in which the silicon atom locates at the ring junction position.

Cited by 5 publications

References 49 publications

Strain‐Driven, Non‐Catalysed Ring Expansion of Silicon Heterocycles

Strain‐Driven, Non‐Catalysed Ring Expansion of Silicon Heterocycles

Rhodium-Catalyzed Hydrolytic Cleavage of the Silicon–Carbon Bond of Silacyclobutanes to Access Silanols

Controllable Si–C Bond Formation from Trihydrosilanes En Route to Synthesis of 1,4-Azasilinanes with Diverse Silyl Functionalities

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