New carbon-carbon bond formation reactions expand our horizon of retrosynthetic analysis for the synthesis complex organic molecules. Although many methods are now available C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds via transition metal-catalyzed cross-coupling alkyl organometallic reagents, direct use readily olefins in a formal fashion hydrocarbonation to make remains be developed. Here we report discovery general process intermolecular reductive coupling unactivated with or aryl...

A copper-promoted trifluoromethylation reaction of aromatic amines is described. This transformation proceeds smoothly under mild conditions and exhibits good tolerance many synthetically relevant functional groups. It provides an alternative approach for the synthesis trifluoromethylated arenes heteroarenes. also constitutes a new example Sandmeyer reaction.

Herein, we described a nickel-catalyzed monofluoroalkenylation through defluorinative reductive cross-coupling of gem-difluoroalkenes with alkyl halides. Key to the success this strategy is combination C–F cleavage halides activation. This reaction enables convenient synthesis large variety functionalized monofluoroalkenes under mild conditions broad functional group compatibility and excellent Z-selectivity. The Ni catalysis (Bpin)2/K3PO4 as terminal reductant promoted efficient...

Synthesis of functionalized <italic>gem</italic>-difluoroalkenes was achieved through nickel-catalyzed allylic defluorinative alkylation trifluoromethyl alkenes with reductive decarboxylation redox-active esters.

Abstract A novel copper‐catalyzed regiodivergent alkylboration of alkenes with bis(pinacolato)diboron and alkyl halides has been developed. The regioselectivity the was controlled by subtle differences in ligand structure. reaction thus enables practical, synthesis two different boronic esters complex structures from a single alkene.

Substantial advances in enantioconvergent C(sp3)–C(sp3) bond formation reactions have been made recent years through the use of transition-metal-catalyzed cross-coupling racemic secondary alkyl electrophiles with organometallic reagents. Herein, we report a general process for asymmetric construction alkyl–alkyl bonds adjacent to heteroatoms, namely, nickel-catalyzed reductive hydroalkylation olefins α-heteroatom phosphorus or sulfur electrophiles. Including readily available olefins, this...

Abstract To increase the reliability and success rate of drug discovery, efforts have been made to C( sp 3 ) fraction avoid flat molecules. -Rich enantiopure amines are most frequently encountered as chiral auxiliaries, synthetic intermediates for pharmaceutical agents bioactive natural products. Streamlined construction aliphatic has long regarded a paramount challenge. Mainstream approaches, including hydrogenation enamines imines, C–H amination, alkylation were applied synthesis with...

Regiodivergent alkyne hydroalkylation to generate different isomers of an alkene from the same starting material would be beneficial; however, it remains a challenge. Herein, we report ligand-controlled cobalt-catalyzed regiodivergent hydroalkylation. The sensible selection bisoxazoline (L1) and pyridine-oxazoline (L8) ligands led reliable predictable protocols that provided (E)-1,2-disubstituted 1,1-disubstituted alkenes with high E/Z stereoselectivity regioisomeric ratio identical terminal...

Site- and enantio-selective alkyl-alkyl bond formation is privileged in the retrosynthetic analysis due to universality of sp3-hybridized carbon atoms organic molecules. Herein, we report a nickel-catalyzed remote asymmetric hydroalkylation alkenyl ethers via synchronous implementation alkene isomerization enantioselective C(sp3)-C(sp3) formation. Regression catalyst structure-activity relationships accelerates rational ligand modification through modular regulation. This reaction has...

Metal-hydride-catalyzed alkene hydroalkylation has been developed as an efficient method for C(sp

Organic nanoparticles of 1,3-diphenyl-5-(2-anthryl)-2- pyrazoline (DAP) ranging in average diameters from 40 to 160 nm were prepared through the reprecipitation method. The particles controlled by variation aging time. We found that DAP exhibit size-dependent optical properties. absorption transitions at lower-energy side experience a bathochromic shift with an increase particle size as result increased intermolecular interactions, while higher-energy bands anthracene split possibly due...

The first copper-catalyzed/promoted sp3-C Suzuki–Miyaura coupling reaction of gem-diborylalkanes with nonactivated electrophilic reagents is reported. Not only 1, 1-diborylalkanes but also some other can be coupled primary alkyl halides, offering a new method for sp3C–sp3C bond formation and, simultaneously, providing strategy the synthesis alkylboronic esters.

A nicked reaction: The title reaction of terminal alkynes with non-activated secondary alkyl iodides and bromides was accomplished for the first time. This provides a new practical approach synthesis substituted (see scheme; cod=cyclo-1,5-octadiene). As service to our authors readers, this journal supporting information supplied by authors. Such materials are peer reviewed may be re-organized online delivery, but not copy-edited or typeset. Technical support issues arising from (other than...

Abstract Organoboron compounds play an irreplaceable role in synthetic chemistry and the related transformations based on unique reactivity of C–B bond are potentially most efficient methods for synthesis organic molecules. The importance multiboron C–C formation function transformation reactions is growing borations activated or nonactivated alkenes have been developed recently. However, introducing directly two boron moieties into terminal sites giving 1,1-diborylalkanes a catalytic...

A copper-catalyzed reductive cross-coupling reaction of nonactivated alkyl tosylates and mesylates with aryl bromides was developed. It provides a practical method for efficient cost-effective construction aryl-alkyl alkyl-alkyl CC bonds stereocontrol from readily available substrates. When used in an intramolecular fashion, the enables convenient access to various substituted carbo- or heterocycles, such as 2,3-dihydrobenzofuran benzochromene derivatives.

A Cu/(NHC)-catalyzed SN2'-selective substitution reaction of allylic electrophiles with gem-diborylalkanes is reported. Different substituted and can be employed in this reaction, various synthetic valuable functional groups tolerated. The asymmetric version was initially researched chiral N-heterocyclic carbene (NHC) ligands.

Regiodivergent alkene functionalization that produces either regioisomer starting from the same raw materials is desirable. Herein, we report a nickel-catalyzed switchable site-selective hydroalkylation. The selection of reaction temperatures leads to protocols provide regiodivergent hydroalkylated products single substrate. This protocol allows convenient synthesis α- and β-branched protected amines, both which are important fields pharmaceutical chemistry biochemistry. In addition,...

Abstract Alkene hydrocarbonation reactions have been developed to supplement traditional electrophile-nucleophile cross-coupling reactions. The branch-selective hydroalkylation method applied a broad range of unactivated alkenes remains challenging. Herein, we report NiH-catalysed proximal-selective access β- or γ-branched alkyl carboxylic acids and β-, γ- δ-branched amines. A iodides bromides with different functional groups can be installed excellent regiocontrol availability for...

2-Deoxy-β-C-glycosides represent an important class of carbohydrates that are present in many bioactive molecules. However, owing to the lack substituents at C2 position, stereoselective synthesis 2-deoxy-β-C-glycosides is highly challenging. Herein, we report a ligand-controlled C-alkyl glycosylation reaction access 2-deoxy-β-C-alkyl glycosides from readily available glycals and alkyl halides. This method exhibits broad substrate scope excellent diastereoselectivity under very mild...

Abstract Cyclopropene hydrofunctionalization has been a promising strategy for accessing multi‐substituted cyclopropanes; however, cyclopropene hydroalkylation remains underdeveloped. Herein, we report low‐valent CoH‐catalyzed facial‐selective to access cyclopropanes. This reaction exhibits broad substrate scope of alkyl halides and cyclopropenes tolerates many functional groups. Moderate‐to‐good facial‐selectivity is obtained without any directing Mechanism studies provide evidence that...

Abstract The transient electron donor–acceptor (EDA) complex has been an emerging area in the photoinduced organic synthesis field, generating radicals without exogenous transition‐metal or dye‐based photoredox catalysts. catalytic platform to form suitable photoactive EDA complexes for photochemical reduction reactions remains underdeveloped. Herein, a general reductive alkylation via strategy is described. A simple yet multifunctional system, triphenylphosphine and iodide salt, promotes...

A copper-catalyzed coupling of arylboronates with primary and secondary benzyl halides β hydrogens or steric hindrance is described.