An Unusual Example of Hypervalent Silicon: A Five-Coordinate Silyl Group Bridging Two Palladium or Nickel Centers through a Nonsymmetrical Four-Center Two-Electron Bond

2013 ◽  
Vol 126 (4) ◽  
pp. 1121-1126 ◽  
Author(s):  
Ainara Nova ◽  
Hee-Won Suh ◽  
Timothy J. Schmeier ◽  
Louise M. Guard ◽  
Odile Eisenstein ◽  
...  
Keyword(s):  
Silyl Group ◽  
Nickel Centers

An Unusual Example of Hypervalent Silicon: A Five-Coordinate Silyl Group Bridging Two Palladium or Nickel Centers through a Nonsymmetrical Four-Center Two-Electron Bond

2013 ◽  
Vol 53 (4) ◽  
pp. 1103-1108 ◽  
Author(s):  
Ainara Nova ◽  
Hee-Won Suh ◽  
Timothy J. Schmeier ◽  
Louise M. Guard ◽  
Odile Eisenstein ◽  
...  
Keyword(s):  
Silyl Group ◽  
Nickel Centers

N-Chlorinative Ring Contraction of 1,4-Dimethoxyphthalazines via a Bicyclization/Ring-Opening Mechanism

Synthesis ◽  
2020 ◽  
Author(s):  
Jeong Kyun Im ◽  
Ilju Jeong ◽  
Jun-Ho Choi ◽  
Won-jin Chung ◽  
ByeongDo Yang ◽  
...  
Keyword(s):  
Ring Opening ◽  
Reaction Conditions ◽  
Ring Contraction ◽  
Silyl Group ◽  
Favorskii Rearrangement ◽  
Mechanistic Analysis ◽  
Group A ◽  
Overall Efficiency ◽  
Trichloroisocyanuric Acid

AbstractAn unprecedented N-chlorinative ring contraction of 1,2-diazines was discovered and investigated with an electrophilic chlorinating reagent, trichloroisocyanuric acid (TCICA). Through optimization and mechanistic analysis, the assisting role of n-Bu4NCl as an exogenous nucleophile was identified, and the optimized reaction conditions were applied to a range of 1,4-dimethoxyphthalazine derivatives. Also, an improvement of overall efficiency was demonstrated by the use of a labile O-silyl group. A bicyclization/ring-opening mechanism, inspired by the Favorskii rearrangement, was proposed and supported by the DFT calculations. Furthermore, the efforts on scope expansion as well as the evaluation of other electrophilic promoters revealed that the newly developed ring contraction reactivity is a unique characteristic of 1,4-dimethoxyphthalazine scaffold and TCICA.

scholarly journals Oligosilanylated Silocanes

Molecules ◽  
2021 ◽  
Vol 26 (1) ◽  
pp. 244
Author(s):  
Mohammad Aghazadeh Meshgi ◽  
Alexander Pöcheim ◽  
Judith Baumgartner ◽  
Viatcheslav V. Jouikov ◽  
Christoph Marschner
Keyword(s):  
Cyclic Voltammetry ◽  
Solid State ◽  
Xrd Analysis ◽  
29Si Nmr ◽  
Single Crystal Xrd ◽  
Substitution Pattern ◽  
Silyl Group ◽  
Steric Factors ◽  
Single Crystal Xrd Analysis ◽  
29Si Nmr Spectroscopy

A number of mono- and dioligosilanylated silocanes were prepared. Compounds included silocanes with 1-methyl-1-tris(trimethylsilyl)silyl, 1,1-bis[tris(trimethylsilyl)silyl], and 1,1-bis[tris(trimethylsilyl)germyl] substitution pattern as well as two examples where the silocane silicon atom is part of a cyclosilane or oxacyclosilane ring. The mono-tris(trimethylsilyl)silylated compound could be converted to the respective silocanylbis(trimethylsilyl)silanides by reaction with KOtBu and in similar reactions the cyclosilanes were transformed to oligosilane-1,3-diides. However, the reaction of the 1,1-bis[tris(trimethylsilyl)silylated] silocane with two equivalents of KOtBu leads to the replacement of one tris(trimethylsilyl)silyl unit with a tert-butoxy substituent followed by silanide formation via KOtBu attack at one of the SiMe3 units of remaining tris(trimethylsilyl)silyl group. For none of the silylated silocanes, signs of hypercoordinative interaction between the nitrogen and silicon silocane atoms were detected either in the solid state. by single crystal XRD analysis, nor in solution by 29Si-NMR spectroscopy. This was further confirmed by cyclic voltammetry and a DFT study, which demonstrated that the N-Si distance in silocanes is not only dependent on the energy of a potential N-Si interaction, but also on steric factors and through-space interactions of the neighboring groups at Si and N, imposing the orientation of the pz(N) orbital relative to the N-Si-X axis.

ChemInform Abstract: DIASTEREOSELECTIVITY IN THE ALKYLATION OF ENOLATES HAVING AN ADJACENT SILYL GROUP

1984 ◽  
Vol 15 (19) ◽  
Author(s):  
W. BERNHARD ◽  
I. FLEMING ◽  
D. WATERSON
Keyword(s):  
Silyl Group

Tandem Transformations Initiated by the Migration of a Silyl Group. Some New Synthetic Applications of Silyloxiranes

Synlett ◽  
1994 ◽  
Vol 1994 (12) ◽  
pp. 985-992 ◽  
Author(s):  
P. Jankowski ◽  
P. Raubo ◽  
J. Wicha
Keyword(s):  
Silyl Group

Palladium-Catalyzed Cyclization of Allylsilanes with Nucleophilic Displacement of the Silyl Group

ChemInform ◽  
2003 ◽  
Vol 34 (2) ◽  
Author(s):  
Giovanni Poli ◽  
Guillaume Prestat
Keyword(s):  
Silyl Group ◽  
Nucleophilic Displacement ◽  
Palladium Catalyzed

1,2-O-Silyl Group Rearrangements in Carbohydrates - Convenient Synthesis of Important Lactose Building Blocks1

Synlett ◽  
1995 ◽  
Vol 1995 (09) ◽  
pp. 925-927 ◽  
Author(s):  
José M. Lassaletta ◽  
Richard R. Schmidt
Keyword(s):  
Silyl Group ◽  
Convenient Synthesis

The Tris(trimethylsilyl)silyl Group in Organic, Coordination and Organometallic Chemistry

ChemInform ◽  
2005 ◽  
Vol 36 (21) ◽  
Author(s):  
A. N. Kornev
Keyword(s):  
Organometallic Chemistry ◽  
Silyl Group

ChemInform Abstract: Silyl Group Transfer in the Cycloaddition Reactions of Silyliminium Salts Derived from Aryl-Substituted Oximes.

ChemInform ◽  
1990 ◽  
Vol 21 (6) ◽  
Author(s):  
A. PADWA ◽  
W. H. DENT ◽  
A. M. SCHOFFSTALL ◽  
P. E. YESKE
Keyword(s):  
Cycloaddition Reactions ◽  
Silyl Group ◽  
Group Transfer
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