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Chemical Structure| 775-12-2 Chemical Structure| 775-12-2

Structure of 775-12-2

Chemical Structure| 775-12-2

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Ewelina Szafoni ; Krzysztof Kuciński ; Grzegorz Hreczycho ;

Abstract: Cobalt complexes featuring triazine-based PNP ligands have proven to be exceptionally active and chemoselective pre-catalysts in facilitating the dehydrogenative coupling between silanes and amines, leading to the synthesis of diverse aminosilanes. Notably, even challenging substrates exhibited high reactivity. The catalyst‘s unique feature of avoiding coupling with tertiary silanes enhances process chemoselectivity. It facilitates a more precise synthesis of silylamines possessing of SiH2−N and SiH−N motifs, overcoming challenges associated with broader reactivity seen in previous systems. In terms of its remarkable chemoselectivity, it is also noteworthy that the catalytic system exhibits both versatility and efficacy in converting substrates with untouched double and triple carbon-carbon bonds. This accomplishment is particularly significant, given previous challenges brought about by the activity of commonly employed catalysts in the competitive hydrosilylation process.

Purchased from AmBeed: ;

Samantha E. Sloane ;

Abstract: The similar nature of the hydrogen atom to its isotope, deuterium, allows for the simple exchange of hydrogen atoms for deuterium atoms in drug molecules to alter the absorption, distribution, metabolism, and excretion properties. Installing the deuterium functionality into a specific site in the molecule is essential. Selective hydrofunctionalization reactions of alkynes and alkenes using the highly reactive catalytic Cu–H species have been well developed, and synthetic organic chemistry methods to selectively incorporate one or two deuterium atoms into the benzylic site of organic compounds, a key metabolic position, are elusive. A Cu–H catalytic approach offers selectivity and reactivity to undergo a transfer hydrodeuteration of alkynes or alkenes. Initiating the reaction development with a transfer hydrogenation protocol demonstrated high chemoselectivity on a diverse array of aryl alkynes. Expanding this method to a transfer deuteration generated aryl alkane products with up to 5 deuterium atoms, 2 of which were located at the benzylic carbon. Preliminary regioselective results were explored, providing 2 deuterium atoms at the benzylic position and 2 hydrogen atoms at the homobenzylic position (Chapter 1). One deuterium atom was installed exclusively into aryl alkanes from aryl alkenes using a transfer hydrodeuteration reaction, and MRR, molecular rotational resonance spectroscopy, was explored as an analytical tool to detect different isotopic species present in the product mixture, confirming the highest selectivity reported to date (Chapter 2). Two deuterium atoms were installed selectively into the benzylic site of aryl alkanes from the transfer hydrodeuteration of aryl alkynes, forming ,-d2-alkane products, including complex small molecules. This was based on the electronic stability of the DTB-DPPBz ligand, which was explored both experimentally and computationally (Chapter 3). Exchanging the silane source for diphenylsilane and eliminating the alcohol allowed for a regio-, stereo-, and chemoselective hydrosilylation of aryl alkynes to be accomplished on biologically relevant small molecules, as well as 4 drug analogues, to access -E_x005f_x0002_vinylsilanes. Additionally, this protocol permitted the selective deuterosilylation reaction to access,-d2- alkane products (Chapter 4). Through extensive reaction development, optimization, and mechanistic exploration, highly selective methods of precision deuteration and hydrosilylation were achieved by using a Cu–H catalytic protocol.

Purchased from AmBeed: ;

Hu, Shicheng ;

Abstract: A catalytic method for the direct electrophilic cyanation of C(sp2)–H nucleophiles with sodium cyanate (NaOCN) is reported. Mechanistic experiments show that under solid-liquid phase transfer, an inorganic cyanate is activated by halide displacement on a halophosphonium. Redox catalysis is enabled by the usage of a strained phosphine (phosphetane) so that catalyst turnover from phosphine oxide to phosphine can be easily achieved by the usage of a terminal hydrosilane reductant. These results demonstrate the feasibility of deoxyfunctionalization of insoluble inorganic salts by PIII/PV=O catalyzed phase transfer activation, as exemplified by C(sp2)-H cyanation with NaOCN as the “CN+” source.

Purchased from AmBeed: ; ; ;

Szafoni, Ewelina ; Kucinski, Krzysztof ; Hreczycho, Grzegorz ;

Abstract: Disclosed is a mild, scalable, and chemoselective cross-dehydrogenative functionalization protocol for the construction of Si−O−Si moieties under cobalt catalysis. The reaction has a broad scope and can be used to synthesize a wide range of silicon building blocks, including challenging dihydrosiloxanes and functionalized silsesquioxanes. Most importantly, the results are placed into context by benchmarking with state-of-the-art methods. Remarkably, the utilized PNP-Co catalyst enables the development of further synthetic strategies such as a one-pot sequential silanolysis/alcoholysis process or unprecedented dehydrocoupling reaction between germanol and hydrosilane.

Keywords: CobaltSilsesquioxanesSiloxanesSilanolsHydrosilanesDehydrogenative coupling

Purchased from AmBeed: ; ; ; ; ; ;

Sydney Moise ;

Abstract: With an increased concern for climate change in the recent years, a significant area of research has been devoted to the reduction of greenhouse gases. Carbon dioxide (CO2) resides in the atmosphere between 300 – 1000 years, making the reduction of the molecule a substantial field of study.1 Amines have been used as CO2 scrubbing agents in literature historically, due to their ability to form bonds to carbon.2 Although studies involving metal catalysts and amines have been reported numerous times, research involving chemical reduction of CO2 using purely amines is scarce. In this paper, amines, in addition to hydride donors and other additives, were used to chemically reduce CO2. Additionally, six ruthenium hydrides were synthesized and were used in combination with amines to electrochemically reduce CO2.

Purchased from AmBeed: ;

Alternative Products

Product Details of [ 775-12-2 ]

CAS No. :775-12-2
Formula : C12H12Si
M.W : 184.31
SMILES Code : C1([SiH2]C2=CC=CC=C2)=CC=CC=C1
MDL No. :MFCD00003002
InChI Key :BPYFPNZHLXDIGA-UHFFFAOYSA-N
Pubchem ID :6327659

Safety of [ 775-12-2 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315
Precautionary Statements:P280

Computational Chemistry of [ 775-12-2 ] Show Less

Physicochemical Properties

Num. heavy atoms 13
Num. arom. heavy atoms 12
Fraction Csp3 0.0
Num. rotatable bonds 2
Num. H-bond acceptors 0.0
Num. H-bond donors 0.0
Molar Refractivity 60.7
TPSA ?

Topological Polar Surface Area: Calculated from
Ertl P. et al. 2000 J. Med. Chem.

0.0 Ų

Lipophilicity

Log Po/w (iLOGP)?

iLOGP: in-house physics-based method implemented from
Daina A et al. 2014 J. Chem. Inf. Model.

2.54
Log Po/w (XLOGP3)?

XLOGP3: Atomistic and knowledge-based method calculated by
XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry

3.55
Log Po/w (WLOGP)?

WLOGP: Atomistic method implemented from
Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.

0.81
Log Po/w (MLOGP)?

MLOGP: Topological method implemented from
Moriguchi I. et al. 1992 Chem. Pharm. Bull.
Moriguchi I. et al. 1994 Chem. Pharm. Bull.
Lipinski PA. et al. 2001 Adv. Drug. Deliv. Rev.

3.88
Log Po/w (SILICOS-IT)?

SILICOS-IT: Hybrid fragmental/topological method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

2.28
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

2.61

Water Solubility

Log S (ESOL):?

ESOL: Topological method implemented from
Delaney JS. 2004 J. Chem. Inf. Model.

-3.77
Solubility 0.0313 mg/ml ; 0.00017 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Soluble
Log S (Ali)?

Ali: Topological method implemented from
Ali J. et al. 2012 J. Chem. Inf. Model.

-3.24
Solubility 0.107 mg/ml ; 0.000582 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Soluble
Log S (SILICOS-IT)?

SILICOS-IT: Fragmental method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

-5.02
Solubility 0.00177 mg/ml ; 0.00000959 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Moderately soluble

Pharmacokinetics

GI absorption?

Gatrointestinal absorption: according to the white of the BOILED-Egg

Low
BBB permeant?

BBB permeation: according to the yolk of the BOILED-Egg

No
P-gp substrate?

P-glycoprotein substrate: SVM model built on 1033 molecules (training set)
and tested on 415 molecules (test set)
10-fold CV: ACC=0.72 / AUC=0.77
External: ACC=0.88 / AUC=0.94

No
CYP1A2 inhibitor?

Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.83 / AUC=0.90
External: ACC=0.84 / AUC=0.91

Yes
CYP2C19 inhibitor?

Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.80 / AUC=0.86
External: ACC=0.80 / AUC=0.87

Yes
CYP2C9 inhibitor?

Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set)
and tested on 2075 molecules (test set)
10-fold CV: ACC=0.78 / AUC=0.85
External: ACC=0.71 / AUC=0.81

No
CYP2D6 inhibitor?

Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set)
and tested on 1068 molecules (test set)
10-fold CV: ACC=0.79 / AUC=0.85
External: ACC=0.81 / AUC=0.87

No
CYP3A4 inhibitor?

Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set)
and tested on 2579 molecules (test set)
10-fold CV: ACC=0.77 / AUC=0.85
External: ACC=0.78 / AUC=0.86

No
Log Kp (skin permeation)?

Skin permeation: QSPR model implemented from
Potts RO and Guy RH. 1992 Pharm. Res.

-4.9 cm/s

Druglikeness

Lipinski?

Lipinski (Pfizer) filter: implemented from
Lipinski CA. et al. 2001 Adv. Drug Deliv. Rev.
MW ≤ 500
MLOGP ≤ 4.15
N or O ≤ 10
NH or OH ≤ 5

0.0
Ghose?

Ghose filter: implemented from
Ghose AK. et al. 1999 J. Comb. Chem.
160 ≤ MW ≤ 480
-0.4 ≤ WLOGP ≤ 5.6
40 ≤ MR ≤ 130
20 ≤ atoms ≤ 70

None
Veber?

Veber (GSK) filter: implemented from
Veber DF. et al. 2002 J. Med. Chem.
Rotatable bonds ≤ 10
TPSA ≤ 140

0.0
Egan?

Egan (Pharmacia) filter: implemented from
Egan WJ. et al. 2000 J. Med. Chem.
WLOGP ≤ 5.88
TPSA ≤ 131.6

0.0
Muegge?

Muegge (Bayer) filter: implemented from
Muegge I. et al. 2001 J. Med. Chem.
200 ≤ MW ≤ 600
-2 ≤ XLOGP ≤ 5
TPSA ≤ 150
Num. rings ≤ 7
Num. carbon > 4
Num. heteroatoms > 1
Num. rotatable bonds ≤ 15
H-bond acc. ≤ 10
H-bond don. ≤ 5

2.0
Bioavailability Score?

Abbott Bioavailability Score: Probability of F > 10% in rat
implemented from
Martin YC. 2005 J. Med. Chem.

0.55

Medicinal Chemistry

PAINS?

Pan Assay Interference Structures: implemented from
Baell JB. & Holloway GA. 2010 J. Med. Chem.

0.0 alert
Brenk?

Structural Alert: implemented from
Brenk R. et al. 2008 ChemMedChem

1.0 alert: heavy_metal
Leadlikeness?

Leadlikeness: implemented from
Teague SJ. 1999 Angew. Chem. Int. Ed.
250 ≤ MW ≤ 350
XLOGP ≤ 3.5
Num. rotatable bonds ≤ 7

No; 1 violation:MW<2.0
Synthetic accessibility?

Synthetic accessibility score: from 1 (very easy) to 10 (very difficult)
based on 1024 fragmental contributions (FP2) modulated by size and complexity penaties,
trained on 12'782'590 molecules and tested on 40 external molecules (r2 = 0.94)

3.55

Application In Synthesis of [ 775-12-2 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 775-12-2 ]

[ 775-12-2 ] Synthesis Path-Downstream   1~12

  • 1
  • [ 67-56-1 ]
  • [ 775-12-2 ]
  • [ 6843-66-9 ]
YieldReaction ConditionsOperation in experiment
99% With potassium hexamethylsilazane; In neat liquid; at 30℃; for 2h;Schlenk technique; Inert atmosphere; General procedure: Catalyzed CDC reactions were carried out using the following standard protocol. In the glove box, the chosen pre-catalyst (0.05 mmol) was loaded into a Schlenk tube, and subsequently the alcohol (n x 0.05 mmol, n equiv.) followed by silane (n' x 0 0.05 mmol, n' equiv.) were added. The reaction mixture was stirred at the desired temperature (30C), which was controlled by an oil bath. After the required period, the reaction was quenched by adding CDCl3 to the mixture. Substrate conversion was monitored by examination of the 1H NMR spectrum of the reaction mixture and comparing relative intensities of resonance characteristics of the substrates and products.
  • 3
  • [ 38430-55-6 ]
  • [ 775-12-2 ]
  • 4-(1-diphenylsilanyloxy-ethyl)-benzoic acid ethyl ester [ No CAS ]
  • 1-(diphenylsiloxy)-1-(4-ethoxycarbonylphenyl)ethene [ No CAS ]
  • 4
  • [ 67-56-1 ]
  • [ 775-12-2 ]
  • [ 40391-85-3 ]
  • [ 6843-66-9 ]
  • 5
  • [ 106-86-5 ]
  • [ 775-12-2 ]
  • 2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyldiphenylsilane [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% General procedure: A typical procedure (Table 2, entry 1) is as follows. To a stirredsolution of Ni(acac)2 (1a) (1.3 mg, 0.005 mmol) in THF (5 mL) wasadded 1-octene (112 mg, 1.0 mmol) and (EtO)3SiH (164 mg,1.0 mmol) at room temperature. After the mixture was stirred for1 min, NaBHEt3 (1.0Min THF, 5 mL, 0.005 mmol) was added and theresulting mixture was heated at 50 C. The solution was stirred atthe same temperature, and the progress of the reaction wasmonitored by GLC. After completion of the reaction, mesitylene(60 mg, 0.50 mmol) was added as an internal standard to the reactionmixture. The GLC analysis of the resulting solution revealedthe formation of (EtO)3(nOct)Si (0.90 mmol, 90%) and (EtO)4Si(0.05 mmol, 5%). The solutionwas concentrated under vacuum, andthe residue was purified by gel permeation chromatography (GPC)using toluene as an eluent to give (EtO)3(nOct)Si (234 mg,0.85 mmol, 85%). The 1H, 13C{1H} and 29Si{1H} NMR spectra of theisolated compound are consistent with the reported data. A similarprocedurewas employed for the hydrosilylation using other silanesand 1,3-diene/alkenes/alkynes. These reactions were carried out atroom temperature except for the reactions, Table 2, entries 2-3.The 1H/13C NMR spectroscopic data for the new compounds aregiven in the supplementary data.
  • 6
  • [ 393-56-6 ]
  • [ 775-12-2 ]
  • (4-diphenylsilanyl-2-fluorophenyl)dimethylamine [ No CAS ]
  • 7
  • [ 124-38-9 ]
  • [ 775-12-2 ]
  • [ 6843-66-9 ]
YieldReaction ConditionsOperation in experiment
With C21H41N3NiP2; In N,N-dimethyl-formamide; at 20 - 60℃; for 36h;Sealed tube; General procedure: [0182] Using tertiary amines, such as Et3N and DABCO (1,4-Diazabicyclo[2.2.2]octane) and imine, such as DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) as the catalysts led to no methanol product (Table 3, entries 4-6). The reaction worked well in polar aprotic solvents such as DMF, THF, and MeCN, with slower reaction rates in THF and MeCN (Table 3, entries 7 and 8), presumably because DIVIF can act as a Lewis base to help to activate silane and thus accelerate the reaction.28 No reaction was observed in CH2C12 and toluene (Table 3, entries 9 and 10). Further screening of catalyst loadings (Table 3, entries 11-16) revealed that diphenylsilane could be fully consumed with a catalyst loading as low as 0.02 mol% (Table 3, entry 16). The turnover number (TON) and turnover frequency (TOF) for hydride 2 as the catalyst in this reaction could reach 4900 and 136 h?, respectively (Table 3, entry 16), much higher than those of the (N-heterocyclic carbene) NHC catalysts.?4 To the best of our knowledge, this is the highest TON and TOF reported for the reduction of CO2 with silane to methanol.[0188] General procedures for reduction of CO2 to methanol: to a fresh vial was added nickel PN3P-pincer complex 2 (4.6 mg, 0.01 mmol), and 1.8 mL of DIVIF was introduced. The vial was sealed, and CO2 was introduced into the vial via a balloon. The reaction was allowed to stir for 30 mm at room temperature, after which diphenylsilane (0.19 mL, 1 mmol) was introduced. The reaction was quenched after 18 h by adding 2 equivalents of NaOH/H20 solution. It was stirred for another 24 h before an aliquot of isopropyl alcohol was added as an internal standard. An aliquot of 0.2 mL was removed from the sample and diluted with dichloromethane before the resulting mixture was subjected to GC analysis.
  • 8
  • [ 6843-66-9 ]
  • [ 25015-63-8 ]
  • [ 694-53-1 ]
  • [ 775-12-2 ]
  • 9
  • [ 6843-66-9 ]
  • [ 40391-85-3 ]
  • [ 775-12-2 ]
  • 10
  • [ 124-38-9 ]
  • [ 775-12-2 ]
  • [ 258267-34-4 ]
  • [ 6843-66-9 ]
YieldReaction ConditionsOperation in experiment
With 1,10-Phenanthroline; zinc diacetate; In [D3]acetonitrile; at 80℃; under 1875.19 Torr; for 24h;Autoclave; Glovebox;Catalytic behavior; Kinetics; Zn(OAc)2 (0.02mmol, 3.7 mg),phen (0.06mmol, 10.8 mg), CD3CN (1 mL), Ph2SiH2 (3mmol,552 mg) were added to an autoclave. The autoclave was sealedtightly, and filled with CO2 to 0.25MPa (initial pressure). After24 h reaction at 80 C, CO2 was released gently, and mesitylenewas added as an internal standard. The solution was then transferredto a J. Young NMR tube for NMR analysis. 1HNMR(400 MHz): 3.6 ppm for CH3OSiR3; 13C{1H}NMR (100 MHz):52 ppm for CH3OSiR3
  • 11
  • [ 1455-20-5 ]
  • [ 775-12-2 ]
  • C20H22SSi [ No CAS ]
  • 12
  • [ 769-26-6 ]
  • [ 775-12-2 ]
  • C23H22Si [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With [{(DIPP-nacnac)CaH(thf)}2]; In toluene; at 100℃; for 15h;Inert atmosphere; Schlenk technique; Sealed tube; General procedure: In a nitrogen-filled glovebox, complex 1 (0.025 mmol), terminal alkyne (0.5 mmol)and silane (1.5 mmol) in toluene (2 mL) were loaded into a 25 mL Schlenk tube. Thistube was sealed, taken out of the glovebox, and put into an oil bath which had beenpreviously set to 100 oC. After completion of the reaction (monitored by 1H NMR), thereaction was quenched by opening to air, and the volatiles of the reaction mixture wereremoved under vacuum at room temperature. The residue was purified by columnchromatography on silica gel to provide alkynylsilane.
 

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