88459-01-2Relevant articles and documents
Copper-Catalyzed Intermolecular Functionalization of Unactivated C(sp3)-H Bonds and Aliphatic Carboxylic Acids
Mao, Runze,Bera, Srikrishna,Turla, Aurélya Christelle,Hu, Xile
supporting information, p. 14667 - 14675 (2021/09/18)
Intermolecular functionalization of C(sp3)-H bonds and aliphatic carboxylic acids enables the efficient synthesis of high value-added organic compounds from readily available starting materials. Although methods involving hydrogen atom transfer have been developed for such functionalization, these methods either work for only activated C(sp3)-H bonds or bring in a narrow set of functional groups. Here we describe a Cu-catalyzed process for the diverse functionalization of both unactivated C(sp3)-H bonds and aliphatic carboxylic acids. The process is enabled by the trapping of alkyl radicals generated through hydrogen atom abstraction by arylsulfonyl-based SOMO-philes, which introduces a large array of C, N, S, Se, and halide-based functional groups. The chemoselectivity can be switched from C-H functionalization to decarboxylative functionalization by matching the bond dissociation energy of the hydrogen atom transfer reagent with that of the target C-H or O-H bond.
Iron-Catalyzed C-C Single-Bond Cleavage of Alcohols
Liu, Wei,Wu, Qiang,Wang, Miao,Huang, Yahao,Hu, Peng
supporting information, p. 8413 - 8418 (2021/11/01)
An iron-catalyzed deconstruction/hydrogenation reaction of alcohols through C-C bond cleavage is developed through photocatalysis, to produce ketones or aldehydes as the products. Tertiary, secondary, and primary alcohols bearing a wide range of substituents are suitable substrates. Complex natural alcohols can also perform the transformation selectively. A investigation of the mechanism reveals a procedure that involves chlorine radical improved O-H homolysis, with the assistance of 2,4,6-collidine.
Dealkenylative Thiylation of C(sp3)-C(sp2) Bonds
Smaligo, Andrew J.,Kwon, Ohyun
supporting information, p. 8592 - 8597 (2019/10/14)
Carbon-carbon bond fragmentations are useful methods for the functionalization of molecules. The value of such cleavage events is maximized when paired with subsequent bond formation. Herein we report a protocol for the cleavage of an alkene C(sp3)-C(sp2) bond, followed by the formation of a new C(sp3)-S bond. This reaction is performed in nonanhydrous solvent and open to the air, employs common starting materials, and can be used to rapidly diversify natural products.
CATALYTIC C-X-BOND METATHESIS THROUGH ARYLATION
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Page/Page column 9; 17, (2018/09/28)
The present invention refers to a process for a catalytic aryl transfer to rearrange the backbone of aromatic C-X bonds.
Nickel Phosphite/Phosphine-Catalyzed C-S Cross-Coupling of Aryl Chlorides and Thiols
Jones, Kieran D.,Power, Dennis J.,Bierer, Donald,Gericke, Kersten M.,Stewart, Scott G.
supporting information, p. 208 - 211 (2018/01/17)
A method for the coupling of aryl chlorides and thiophenols using an air-stable nickel(0) catalyst is described. This thioetherification procedure can be effectively applied to a range of electronically diverse aryl/heteroaryl chlorides without more expensive metal catalysts such as palladium, iridium, or ruthenium. This investigation also illustrates both, a variety of thiol coupling partners and, in certain cases, the use of Cs2CO3.
Catalytic B(C6F5)3[rad]H2O-promoted defluorinative functionalization of tertiary aliphatic fluorides
Dryzhakov, Marian,Richmond, Edward,Li, Guang,Moran, Joseph
, p. 45 - 51 (2016/12/06)
A B(C6F5)3[rad]H2O-catalyzed defluorinative functionalization of tertiary aliphatic fluorides is described that proceeds under benign reaction conditions. The synthetic utility of the method is exemplified throu
A comparative study of Cu(II)-assisted vs Cu(II)-free chalcogenation on benzyl and 2°/3°-cycloalkyl moieties
Sahoo, Santosh K
, p. 2151 - 2157 (2016/01/12)
A relative synthetic strategy toward intermolecular oxidative C -Chalcogen bond formation of alkanes has been illustrated using both Cu(II) assisted vs Cu(II) free conditions. This led to construction of a comparative study of hydrocarbon benzylic and 2°/ 3°-cycloalkyl moieties bond sulfenylation and selenation protocol by the chalcogen sources, particularly sulfur and selenium, respectively. In addition, this protocol disclosed the auspicious formation of sp3 C-S coupling products over leading the sp3 C-N coupling products by using 2-mercaptobenzothiazole (MBT) substrates.
Synthesis of substituted adamantylzinc reagents using a Mg-insertion in the presence of ZnCl2 and further functionalizations
Saemann, Christoph,Dhayalan, Vasudevan,Schreiner, Peter R.,Knochel, Paul
supporting information, p. 2418 - 2421 (2014/05/20)
The LiCl-mediated Mg-insertion in the presence of ZnCl2 allows an efficient synthesis of adamantylzinc reagents starting from the corresponding functionalized tertiary bromides. The highly reactive adamantylzinc species readily undergo a broad
Silver-mediated decarboxylative C-S cross-coupling of aliphatic carboxylic acids under mild conditions
Wang, Peng-Fei,Wang, Xiao-Qing,Dai, Jian-Jun,Feng, Yi-Si,Xu, Hua-Jian
supporting information, p. 4586 - 4589 (2015/01/08)
A silver-mediated decarboxylative C-S cross-coupling reaction of aliphatic carboxylic acid is described. This reaction occurs smoothly under mild conditions and shows good tolerance of functional groups. It provides an alternative approach for the synthesis of alkyl aryl sulfides.
Syntheses of sulfides and selenides through direct oxidative functionalization of C(sp3)-H bond
Du, Bingnan,Jin, Bo,Sun, Peipei
supporting information, p. 3032 - 3035 (2014/06/23)
A new protocol for C-S and C-Se bond formation by the direct functionalization of the C(sp3)-H bond of alkanes under metal-free conditions was developed. Using tBuOOtBu as the oxidant, the reaction of disulfides or diselenides with alkanes gave sulfides or selenides in moderate to good yields. The method was very simple and atom-economical.
