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 7 publications

(2 citation statements)

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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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Synthesis of 2,2,3,3‐Tetraphenyl‐5,5,6,6,7,7,8,8‐octamethyl‐2,3,5,6,7,8‐hexasilabicyclo[2.2.2]octane – a Phenyl‐substituted Silicon‐containing Cage

Sato,

Sasamori

2024

Zeitschrift anorg allge chemie

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Molecular cages that contain silicon are highly versatile and stable materials with great potential for various scientific and technological applications due to their ability to form stable three‐dimensional frameworks. The synthesis of 2,2,3,3,5,5,6,6,7,7,8,8‐dodecamethyl‐2,3,5,6,7,8‐hexasilabicyclo[2.2.2]octane has already been reported and its modifications at the CH moiety have been demonstrated to afford varied functionality. Here, we present the synthesis and characterization of 2,2,3,3‐tetraphenyl‐5,5,6,6,7,7,8,8‐octamethyl‐2,3,5,6,7,8‐hexasilabicyclo[2.2.2]octane, which is a phenyl‐substituted analogue of such a silicon‐containing cage. The Ph‐substituted Si‐containing cage exhibits a low‐lying LUMO due to the hyper‐conjugation including Si–Si, Si–C σ*‐orbitals, and π(phenyl)‐orbitals, which results in a remarkable bathochromic shift in the UV‐vis absorption spectrum.

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