A nitrile-based template that enables meta-selective C–H bond functionalization was developed. The is applicable to a range of substituted arenes and tolerates variety functional groups. directing group uses silicon atom for attachment, allowing facile introduction/deprotection strategy increasing the synthetic practicality this template.

The activation of olefins for asymmetric chemical synthesis traditionally relies on transition metal catalysts. In contrast, biological enzymes with Brønsted acidic sites appropriate strength can protonate and thereby generate carbocations that ultimately react to form natural products. Although chemists have recently designed chiral acid catalysts activate imines carbonyl compounds, mimicking these simple then engage in catalytic reactions has remained a substantial synthetic challenge....

A direct enantioselective synthesis of substituted oxygen heterocycles from lactol acetates and enolsilanes has been realized using a highly reactive confined imidodiphosphorimidate (IDPi) catalyst. Various chiral heterocycles, including tetrahydrofurans, tetrahydropyrans, oxepanes, chromans, dihydrobenzofurans, were obtained in excellent enantioselectivities by reacting the corresponding with diverse enol silanes. Mechanistic studies suggest reaction to proceed via nonstabilized, aliphatic,...

Reactions that form a product with the same reactive functionality as of one starting compounds frequently end in oligomerization. As salient example, selective aldol coupling smallest, though arguably most useful, enolizable aldehyde, acetaldehyde, just partner substrate has proven to be extremely challenging. Here, we report highly enantioselective Mukaiyama reaction simple triethylsilyl (TES) and tert-butyldimethylsilyl (TBS) enolates acetaldehyde various aliphatic aromatic acceptor...

We describe the design and development of first catalytic asymmetric vinylogous Prins cyclization. This reaction constitutes an efficient approach for highly diastereo- enantioselective synthesis tetrahydrofurans (THFs) is catalyzed by a confined chiral imidodiphosphoric acid (IDP). Aromatic heteroaromatic aldehydes react with various 3,5-dien-1-ols to afford 2,3-disubstituted THFs in excellent selectivity (d.r. > 20:1, e.r. up 99:1). Aliphatic similarly results when acidic...

The enantioselective allylation of aldehydes to form homoallylic alcohols is one the most frequently used carbon–carbon bond-forming reaction in chemical synthesis and, for several decades, has been a testing ground new asymmetric methodology. However, general and highly catalytic addition inexpensive, nontoxic, air- moisture-stable allyltrimethylsilane aldehydes, Hosomi–Sakurai1 reaction, remained elusive.2, 3 Reported herein design acidic imidodiphosphorimidate motif (IDPi), which enables...

Abstract The combination of a high‐Ni LiNi x Mn y Co 1− − O 2 (NMC) cathode and Li metal anode is currently considered the most promising candidate for high‐energy‐density Li‐metal batteries. However, undesired parasitic reactions in LiPF 6 ‐based carbonate electrolytes hinder their further application. Herein, we report new fluorinated linear additive, ethyl 2‐(2‐fluoroethoxy)ethyl carbonate) (EFEEC), to lithium bis(trifluoromethanesulfonyl) imide–lithium bis(oxalate)borate‐based dual‐salt...

Amine carboxyborane enabled an efficient halogen atom transfer (XAT) with 1 o , 2 and 3 alkyl bromides, resulting in Giese addition products various electron-deficient double bonds. Moreover, direct of...

Abstract O‐heterocycles bearing tetrasubstituted stereogenic centers are prepared via catalytic chemo‐ and enantioselective nucleophilic additions to ketoaldehydes, in which the ketone reacts preferentially over aldehyde. Five‐ six‐membered rings with both aromatic aliphatic substituents, as well an alkynyl substituent, obtained. Moreover, 2,2,5‐trisubstituted 2,2,5,5‐tetrasubstituted tetrahydrofurans synthesized excellent stereoselectivities. Additionally, synthetic utility of described...

Readily available hexyl silane is an excellent choice as a H-atom donor and chain carrier in Lewis acid mediated enantioselective radical reactions. Conjugate additions to alpha,beta-unsaturated imides at room temperature proceed good yields enantioselectivities.

Herein we report the site-selective silylation of ribonucelosides. The method enables a simple and efficient procedure for accessing suitably protected monomers automated RNA synthesis. Switching to opposite enantiomer catalyst allows selective 3′-hydroxyl, which could be used in synthesis unnatural or analoging Lastly, was extended ribavirin potent antiviral therapeutic.

Strong and confined imidodiphosphorimidate (IDPi) catalysts enable highly enantioselective substitutions of cyclic, aliphatic hemiaminal ethers with enol silanes. 2-Substituted pyrrolidines, piperidines, azepanes are obtained high enantioselectivities, the method displays a broad tolerance various silane nucleophiles. Several natural products can be accessed using this methodology. Mechanistic studies support intermediacy non-stabilized, cyclic N-(exo-acyl)iminium ions, paired chiral...

The strong C–H bond activation of hydrocarbons is a difficult reaction in environmental and biological chemistry. Herein, high-valent manganese(IV)-hydroxo complex, [MnIV(CHDAP-O)(OH)]2+ (2), was synthesized characterized by various physicochemical measurements, such as ultraviolet–visible (UV–vis), electrospray ionization-mass spectrometry (ESI-MS), electron paramagnetic resonance (EPR), helium-tagging infrared photodissociation (IRPD) methods. one-electron reduction potential (Ered) 2...

Abstract An unprecedented correlation between the catalytic activity of a Zr‐based UiO‐type metal‐organic framework (MOF) and its degree interpenetration (DOI) is reported. The DOI an MOF hard to control owing high‐energy penalty required construct partially interpenetrated structure. Surprisingly, strong interactions building blocks (inter‐ligand hydrogen bonding) facilitate formation structures under carefully regulated synthesis conditions. Moreover, conversion rates for cyanosilylation...

Herein, we report a mild and practical method for the deuteration of alkyl aryl bromides by thiyl radical catalyst halogen-atom transfer (XAT) using disulfides silanes under visible-light irradiation.

Ketyl radicals are synthetically versatile reactive species, but their applications have been hampered by harsh generation conditions employing highly reducing metals. Recently, the pyridine-boryl radical received wide attention as a promising organic reductant because of its mildness well convenience in handling. While probing utility radical, our group observed facile pinacol coupling reactivity that had not known at time. This serendipitous finding was successfully rendered into practical...

Abstract We report a one‐pot sulfa‐Michael addition reaction using disulfide and pyridine‐borane complex under blue light irradiation. This novel synthetic approach has broad substrate scope high functional group tolerance. Mechanistic studies suggest that sequential radical ionic processes provide practical solution for constructing carbon–sulfur bonds.

We describe meta-selective C-H functionalization of arylsilanes using a Si-tethered directing group. The current method enables selective alkenylation arenes bearing variety functional groups, and several electron-deficient olefins are also applicable as coupling partners. Further group transformations the silicon-tethered provide multisubstituted efficiently.

Enantioselective conjugate radical addition to alpha'-hydroxy alpha,beta-unsaturated ketones, compounds containing bidentate donors, has been investigated. It found that additions ketones in the presence of Mg(NTf2)2 and bisoxazoline ligand 5a proceeded cleanly, yielding products high chemical yields good enantiomeric excesses.

A series of cobalt(III)-peroxo complexes, [CoIII(R2-TBDAP)(O2)]+ (1R2; R2 = Cl, H, and OMe), cobalt(III)-hydroperoxo [CoIII(R2-TBDAP)(O2H)(CH3CN)]2+ (2R2), bearing electronically tuned tetraazamacrocyclic ligands (R2-TBDAP N,N'-di-tert-butyl-2,11-diaza[3.3](2,6)-p-R2-pyridinophane) were prepared from their cobalt(II) precursors characterized by various physicochemical methods. The X-ray diffraction spectroscopic analyses unambiguously showed that all 1R2 compounds have similar octahedral...

Catalytic enantioselective radical conjugate addition reactions using alpha'-phosphoric enone templates have been studied. The C 2-symmetric bisoxazoline-zinc(II) complex proves to be effective for high enantioselectivities and chemical yields. In addition, intermediate alpha-carbonyl alkyl radicals could trapped with allyltributylstannane afford anti-isomers as major products enantioselectivities.