Month: December 2022

Shu, Chao published the artcilePhotoredox-Catalyzed Cyclobutane Synthesis by a Deboronative Radical Addition-Polar Cyclization Cascade, SDS of cas: 238088-16-9, the publication is Angewandte Chemie, International Edition (2019), 58(12), 3870-3874, database is CAplus and MEDLINE.

Photoredox-catalyzed methylcyclobutanations of boronic esters are described. The reactions proceed through single-electron transfer induced deboronative radical addition to an electron-deficient alkene followed by single-electron reduction and polar 4-exo-tet cyclization with a pendant alkyl halide. Key to the success of the methodol. was the use of easily oxidizable arylboronate complexes. Structurally diverse cyclobutanes are shown to be conveniently prepared from readily available boronic esters and a range of haloalkyl alkenes. The mild reactions display excellent functional group tolerance, and the radical addition-polar cyclization cascade also enables the synthesis of 3-, 5-, 6-, and 7-membered rings.

Angewandte Chemie, International Edition published new progress about 238088-16-9. 238088-16-9 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Boronic acid and ester,Aliphatic cyclic hydrocarbon,Boronic Acids,Boronate Esters, name is 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)butanenitrile, and the molecular formula is C11H10O3, SDS of cas: 238088-16-9.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Shu, Chao published the artcileMetal-free photoinduced C(sp³)-H borylation of alkanes, Recommanded Product: 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)butanenitrile, the publication is Nature (London, United Kingdom) (2020), 586(7831), 714-719, database is CAplus and MEDLINE.

Boronic acids and their derivatives are some of the most useful reagents in the chem. sciences, with applications spanning pharmaceuticals, agrochems. and functional materials. Catalytic C-H borylation is a powerful method for introducing these and other boron groups into organic mols. because it can be used to directly functionalize C-H bonds of feedstock chems. without the need for substrate pre-activation. These reactions have traditionally relied on precious-metal catalysts for C-H bond cleavage and, as a result, display high selectivity for borylation of aromatic C(sp²)-H bonds over aliphatic C(sp³)-H bonds. Here we report a mechanistically distinct, metal-free borylation using hydrogen atom transfer catalysis, in which homolytic cleavage of C(sp³)-H bonds produces alkyl radicals that are borylated by direct reaction with a diboron reagent. The reaction proceeds by violet-light photoinduced electron transfer between an N-alkoxyphthalimide-based oxidant and a chloride hydrogen atom transfer catalyst. Unusually, stronger Me C-H bonds are borylated preferentially over weaker secondary, tertiary and even benzylic C-H bonds. Mechanistic studies indicate that the high Me selectivity is a result of the formation of a chlorine radical-boron ‘ate’ complex that selectively cleaves sterically unhindered C-H bonds. By using a photoinduced hydrogen atom transfer strategy, this metal-free C(sp³)-H borylation enables unreactive alkanes to be transformed into valuable organoboron reagents under mild conditions and with selectivities that contrast with those of established metal-catalyzed protocols.

Nature (London, United Kingdom) published new progress about 238088-16-9. 238088-16-9 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Boronic acid and ester,Aliphatic cyclic hydrocarbon,Boronic Acids,Boronate Esters, name is 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)butanenitrile, and the molecular formula is C3H9ClOS, Recommanded Product: 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)butanenitrile.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Sang, Ruocheng published the artcileChiral Benzothiophene Synthesis via Enantiospecific Coupling of Benzothiophene S-Oxides with Boronic Esters, Quality Control of 238088-16-9, the publication is Angewandte Chemie, International Edition (2021), 60(48), 25313-25317, database is CAplus and MEDLINE.

Benzothiophenes are valuable heterocycles that are widely used in medicines, agrochems., and materials science. Herein, a general method for the synthesis of enantioenriched 2,3-disubstituted benzothiophenes via a transition-metal-free C2-alkylation of benzothiophenes with boronic esters is reported. The reactions utilize benzothiophene S-oxides in lithiation-borylations to generate intermediate arylboronate complexes, and subsequent Tf₂O-promoted S-O bond cleavage to trigger a Pummerer-type 1,2-metalate shift, which gives the coupled products with complete enantiospecificity. Primary, secondary and tertiary alkyl boronic esters and aryl boronic esters are successfully coupled with a range of C3-substituted benzothiophenes. Importantly, this transformation does not require the use of C3 directing groups, therefore it overcomes a major limitation of previously developed transition-metal-mediated C2 alkylations of benzothiophenes.

Angewandte Chemie, International Edition published new progress about 238088-16-9. 238088-16-9 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Boronic acid and ester,Aliphatic cyclic hydrocarbon,Boronic Acids,Boronate Esters, name is 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)butanenitrile, and the molecular formula is C10H18BNO2, Quality Control of 238088-16-9.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Ohishi, Takeshi published the artcileCarboxylation of organoboronic esters catalyzed by N-heterocyclic carbene copper(I) complexes, Synthetic Route of 214360-44-8, the publication is Angewandte Chemie, International Edition (2008), 47(31), 5792-5795, database is CAplus and MEDLINE.

N-heterocyclic carbene copper(I) complexes serve as excellent catalysts for the carboxylation of aryl- and alkenylboronic esters with CO₂, affording a variety of functionalized carboxylic acid derivatives Important active intermediates such as the copper(I) aryl and carboxylate complexes, [(IPr)CuR] and [(IPr)CuOCOR] (R = 4-MeOC₆H₄, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), are isolated and structurally characterized.

Angewandte Chemie, International Edition published new progress about 214360-44-8. 214360-44-8 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Boronic acid and ester,Benzene,Boronic Acids,Boronic acid and ester, name is 4-(5,5-Dimethyl-1,3,2-dioxaborinan-2-yl)benzonitrile, and the molecular formula is C12H14BNO2, Synthetic Route of 214360-44-8.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Suzuki, Kensuke published the artcile(o-Phenylenediamino)borylstannanes: Efficient Reagents for Borylation of Various Alkyl Radical Precursors, SDS of cas: 238088-16-9, the publication is Chemistry – A European Journal (2021), 27(12), 3968-3973, database is CAplus and MEDLINE.

(o-Phenylenediamino)borylstannanes were newly synthesized to achieve radical boryl substitutions of a variety of alkyl radical precursors. Dehalogenative, deaminative, dechalcogenative, and decarboxylative borylations proceeded in the presence of a radical initiator to give the corresponding organic B compounds Radical clock experiments and computational studies provided insights into the mechanism of the homolytic substitution (S_H2) of the borylstannanes with alkyl radical intermediates. DFT calculation disclosed that the phenylenediamino structure lowered the LUMO level including the vacant p-orbital on the B atom to enhance the reactivity to alkyl radicals in S_H2. Also, C(sp³)-H borylation of THF was accomplished using the triplet state of xanthone.

Chemistry – A European Journal published new progress about 238088-16-9. 238088-16-9 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Boronic acid and ester,Aliphatic cyclic hydrocarbon,Boronic Acids,Boronate Esters, name is 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)butanenitrile, and the molecular formula is C14H23N, SDS of cas: 238088-16-9.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Moon, Sanghun published the artcileThioether-Directed Peri-Selective C-H Arylation under Rhodium Catalysis: Synthesis of Arene-Fused Thioxanthenes, Safety of 4-(5,5-Dimethyl-1,3,2-dioxaborinan-2-yl)benzonitrile, the publication is Organic Letters (2019), 21(1), 233-236, database is CAplus and MEDLINE.

A rhodium-catalyzed direct C-H arylation of naphthalene and anthracene was developed with the assistance of a thioether directing group. The reaction proceeded with exclusive peri-selectivity, and the series of coupling products were readily transformed into the corresponding sulfur-containing polyaromaticse.g., I (X-rays single crystal structure shown). Charge-transport properties of the provided dithiapyrenes were evaluated by computational studies.

Organic Letters published new progress about 214360-44-8. 214360-44-8 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Boronic acid and ester,Benzene,Boronic Acids,Boronic acid and ester, name is 4-(5,5-Dimethyl-1,3,2-dioxaborinan-2-yl)benzonitrile, and the molecular formula is C12H14BNO2, Safety of 4-(5,5-Dimethyl-1,3,2-dioxaborinan-2-yl)benzonitrile.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Stairs, Shaun published the artcileDivergent prebiotic synthesis of pyrimidine and 8-oxo-purine ribonucleotides, Name: 2-Aminomalononitrile 4-methylbenzenesulfonate, the publication is Nature Communications (2017), 15270, database is CAplus and MEDLINE.

Understanding prebiotic nucleotide synthesis is a long standing challenge thought to be essential to elucidating the origins of life on Earth. Recently, remarkable progress has been made, but to date all proposed syntheses account sep. for the pyrimidine and purine ribonucleotides; no divergent synthesis from common precursors has been proposed. Moreover, the prebiotic syntheses of pyrimidine and purine nucleotides that have been demonstrated operate under mutually incompatible conditions. Here, we tackle this mutual incompatibility by recognizing that the 8-oxo-purines share an underlying generational parity with the pyrimidine nucleotides. We present a divergent synthesis of pyrimidine and 8-oxo-purine nucleotides starting from a common prebiotic precursor that yields the β-ribo-stereochem. found in the sugar phosphate backbone of biol. nucleic acids. The generational relationship between pyrimidine and 8-oxo-purine nucleotides suggests that 8-oxo-purine ribonucleotides may have played a key role in primordial nucleic acids prior to the emergence of the canonical nucleotides of biol.

Nature Communications published new progress about 5098-14-6. 5098-14-6 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Salt,Sulfonic acid,Amine,Benzene, name is 2-Aminomalononitrile 4-methylbenzenesulfonate, and the molecular formula is C8H6ClF3, Name: 2-Aminomalononitrile 4-methylbenzenesulfonate.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

August, David P. published the artcileMaximizing Coordination Capsule-Guest Polar Interactions in Apolar Solvents Reveals Significant Binding, Formula: C10H12F6N4O6PdS2, the publication is Angewandte Chemie, International Edition (2016), 55(48), 15022-15026, database is CAplus and MEDLINE.

Guest encapsulation underpins the functional properties of self-assembled capsules yet identifying systems capable of strongly binding small organic mols. in solution remains a challenge. Most coordination capsules rely on the hydrophobic effect to ensure effective solution-phase association In contrast, we show that using non-interacting anions in apolar solvents can maximize favorable interactions between a cationic Pd₂L₄ host and charge-neutral guests resulting in a dramatic increase in binding strength. With quinone-type guests, association constants in excess of 10⁸ M^-1 were observed, comparable to the highest previously recorded constant for a metallosupramol. capsule. Modulation of optoelectronic properties of the guests was also observed, with encapsulation either changing or switching-on luminescence not present in the bulk phase.

Angewandte Chemie, International Edition published new progress about 68569-14-2. 68569-14-2 belongs to nitriles-buliding-blocks, auxiliary class Palladium, name is Tetrakis(acetonitrile)palladium(II) Ditriflate, and the molecular formula is C10H12F6N4O6PdS2, Formula: C10H12F6N4O6PdS2.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Wentrup, Curt published the artcile3-pyridylnitrene, 2- and 4-pyrimidinylcarbenes, 3-quinolylnitrenes and 4-quinazolinylcarbenes. Interconversion, ring expansion to diazacycloheptatetraenes, ring opening to nitrile ylides and ring contraction to cyanopyrroles and cyanoindoles, Synthetic Route of 26187-28-0, the publication is Beilstein Journal of Organic Chemistry (2013), 743-753, database is CAplus and MEDLINE.

Precursors of 3-pyridylnitrene and 2- and 4-pyrimidinylcarbenes all afford mixtures of 2- and 3-cyanopyrroles on flash vacuum thermolysis, but 3-cyanopyrroles are the first-formed products. 3-Quinolylnitrenes and 4-quinazolinylcarbenes similarly afford 3-cyanoindoles. 2-Pyrimidinylcarbenes rearrange to 3-pyridylnitrenes, but 4-pyrimidinylcarbenes and 4-quinazolinylcarbenes do not necessarily rearrange to the corresponding 3-pyridylnitrenes or 3-quinolylnitrenes. The ring contraction reactions are interpreted in terms of ring opening of either the nitrenes or the diazacycloheptatetraenes to nitrile ylides.

Beilstein Journal of Organic Chemistry published new progress about 26187-28-0. 26187-28-0 belongs to nitriles-buliding-blocks, auxiliary class Pyrrole,Nitrile, name is 2,4-Dimethyl-1H-pyrrole-3-carbonitrile, and the molecular formula is C2H2N4O2, Synthetic Route of 26187-28-0.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Boursalian, Gregory B. published the artcilePd-Catalyzed Aryl C-H Imidation with Arene as the Limiting Reagent, Application In Synthesis of 68569-14-2, the publication is Journal of the American Chemical Society (2013), 135(36), 13278-13281, database is CAplus and MEDLINE.

An amine-N-oxide-ligated palladium complex, in conjunction with a silver cocatalyst, catalyzes imidation of arenes by the reagent N-fluorobenzenesulfonimide. The reaction enables imidation of a variety of arenes at or below room temperature, requires no coordinating directing group on the substrate, and gives synthetically useful yields with only 1 equiv of arene. Mechanistic data implicate an unusual mechanism devoid of commonly invoked organometallic intermediates: oxidation of the Pd catalyst occurs as the turnover-limiting step, while C-H bond functionalization occurs subsequently at a high oxidation state of the catalyst.

Journal of the American Chemical Society published new progress about 68569-14-2. 68569-14-2 belongs to nitriles-buliding-blocks, auxiliary class Palladium, name is Tetrakis(acetonitrile)palladium(II) Ditriflate, and the molecular formula is C10H12F6N4O6PdS2, Application In Synthesis of 68569-14-2.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts