Reactions of an Isolable Dialkylsilylene with Aroyl Chlorides. A New Route to Aroylsilanes

Xiao, Xu‐Qiong; Liu, Xupeng; Lü, Qianqian; Li, Zhifang; Lai, Guoqiao; Kira, Mitsuo

doi:10.3390/molecules21101376

Cited by 7 publications

(8 citation statements)

References 56 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The distance of the Sn(1)–Cl(1) (2.394(2) Å) bond is longer than that of chloro(triphenyl)tin (2.35 Å), but shorter than those of trialkyl derivatives such as Cy 3 SnCl (2.4558 Å, Cy = cyclohexyl) and Me 3 SnCl (2.43 Å) . The C(17)O(1) bond distance of 1.192(7) Å is significantly shorter than those of the corresponding acyl(chloro)silanes ( D , 1.217–1.223 Å) …”

Section: Resultsmentioning

confidence: 96%

“…We have recently reported a similar insertion of an isolable dialkylsilylene as a conventional synthetic method for the corresponding acyl(chloro)silanes D (Chart ). During the course of our studies of the reactions of isolable dialkylstannylene 1 (Chart ) with various functional groups, we have found that the stannylene inserts exclusively into the C–Cl bonds of acyl chlorides, providing a number of acyl(chloro)stannanes that are difficult to synthesize via conventional methods. They are expected to be more reactive than the corresponding acylsilanes and to serve as better synthetic reagents.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Insertion of an Isolable Dialkylstannylene into C–Cl Bonds of Acyl Chlorides Giving Acyl(chloro)stannanes

et al. 2017

Self Cite

View full text Add to dashboard Cite

The reactions of isolable dialkylstannylene 1 with 1-adamantanoyl, 2,2-dimethylpropanoyl, benzoyl, and substituted benzoyl chlorides afford the corresponding acyl(chloro)stannanes in good yields. Similar reactions with more reactive acetyl and propanoyl chlorides do not give the corresponding insertion products but the corresponding dichlorostannane by the overreaction. The benzoyl(chloro)stannane reacts with acetyl chloride to afford the corresponding 1,2-dione and the dichlorostannane quantitatively. Acyl(chloro)stannanes obtained were fully characterized by multinuclear NMR spectroscopy, high-resolution mass spectrometry, and by single-crystal X-ray diffraction studies.

show abstract

Section: Resultsmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Insertion of an Isolable Dialkylstannylene into C–Cl Bonds of Acyl Chlorides Giving Acyl(chloro)stannanes

et al. 2017

Self Cite

View full text Add to dashboard Cite

show abstract

“…Acyl chlorides were also used as a chloride source to react with germylene and stannylenes, in which the corresponding acylgermanes and acylstannanes have been obtained undergoing an insertion of acyl-Cl bond. [50][51][52] While the reaction of 3a with acetyl chloride 8 was carried out at ambient temperature giving the chlorogoldgermane 9 in 67% together with acetyl(triemethylphosphine)gold (Fig. 7a).…”

Section: Full Textmentioning

confidence: 99%

Unique Digoldgermanes: Structural Characteristics, Dynamic Behaviour and Distinctive Reactions

Wang

Zhen

et al. 2021

Preprint

Self Cite

View full text Add to dashboard Cite

Digoldgermanes with a gold coordinated by a dialkylgermylene ligand, R’2Ge(AuPR3)(AuGeR’2) (3a; R = Me, 3b; R = Et), were synthesized as green solids through the reactions of stable dialkylgermylene 1 with R3PAuCl followed by the reduction with KC8 at ambient temperatures. The structural characteristics of 3a and 3b were elucidated using NMR spectroscopy, X-ray crystallography, and DFT calculations. An intense absorption maximum was observed at 590 nm in the UV-vis spectrum of 3a in hexane. A pendular motion of AuPR3 group between Ge(IV) and Ge(II) of 3a and 3b occurring in the NMR time scale was found by the dynamic 1H NMR analysis, suggesting that the Ge(II) ligand has an enhanced electrophilicity to be attacked by the nucleophilic gold atom which closes to ‒1 oxidation state. DFT calculations of 3a revealed the existence of high-lying σ(Ge-Au) type HOMO and low-lying LUMO with germylene pπ nature. We show the bond formation and activation alternatively at Au or Ge atom, a methylation of digoldgermane 3a with MeOTf affords methylgermane 5. Moreover, the digoldgermane 3a reacts with Cl− ion of Ph4PCl and CH3C(O)Cl smoothly to form the corresponding chloride-addition product 7 and chlorogoldgermane 9, respectively. Cyclic trimerization reactions of aromatic isocyanates were high-efficiently catalyzed by 3a giving the corresponding 1,3,5-triaryl isocyanurates.

show abstract

“…In 2016, Kira's group reported the synthesis of acylsilanes by the reaction of dialkylsilylene with benzoyl and aromatic acyl chloride (Scheme 24). [35] During the stipulated mechanism, the reactions started from the formation of acylsilane-silylene complex followed by the formation of a three-membered ring transition state through the concerted mechanism to generate the acylsilanes. Alternatively, silylene played a vital role as a Lewis acid to activate the CÀ Cl bond after the formation of acylsilane-silylene complex to access to the thermally stable acylsilanes in high yields.…”

Section: The Silylation Of Carboxylic Acids or Carboxylic Acid Derivamentioning

confidence: 99%

“…In 2016, Kira's group reported the synthesis of acylsilanes by the reaction of dialkylsilylene with benzoyl and aromatic acyl chloride (Scheme ) . During the stipulated mechanism, the reactions started from the formation of acylsilane‐silylene complex followed by the formation of a three‐membered ring transition state through the concerted mechanism to generate the acylsilanes.…”

Section: The Synthesis Of Acylsilanesmentioning

confidence: 99%

Recent Advances in the Synthesis of Acylsilanes

Wang

Liu

et al. 2020

ChemCatChem

View full text Add to dashboard Cite

Acylsilanes are of wide interest and have been investigated as an important class of organic reaction intermediates with superior chemical and physical properties. Various synthetic methods for the preparation of acylsilanes with mild reaction conditions resulting in excellent yields and high stereoselectiv-ity have been developed. These strategies mainly include stepwise reaction design, oxidative systems, isomerization/rearrangement, silylation of carboxylic acid derivatives and carbonylation. This minireview summarizes recent advances in the synthesis of acylsilanes over the past decade.

show abstract

Reactions of an Isolable Dialkylsilylene with Aroyl Chlorides. A New Route to Aroylsilanes

Cited by 7 publications

References 56 publications

Insertion of an Isolable Dialkylstannylene into C–Cl Bonds of Acyl Chlorides Giving Acyl(chloro)stannanes

Insertion of an Isolable Dialkylstannylene into C–Cl Bonds of Acyl Chlorides Giving Acyl(chloro)stannanes

Unique Digoldgermanes: Structural Characteristics, Dynamic Behaviour and Distinctive Reactions

Recent Advances in the Synthesis of Acylsilanes

Contact Info

Product

Resources

About