Allylboration of ketones with γ-disubstituted allylboronic acids is performed in the presence chiral BINOL derivatives. The reaction suitable for single-step creation adjacent quaternary stereocenters high selectivity. We show that, an appropriate choice catalyst and stereoisomeric prenyl substrate, full control stereo- enantioselectivity possible reaction.

An electrophilic, imide-based, visible-light-promoted photoredox/Ni-catalyzed cross-coupling reaction for the synthesis of aliphatic ketones has been developed. This protocol proceeds through N–C(O) bond activation, made possible lower activation energy metal insertion into this due to delocalization lone pair electrons on nitrogen by electron-withdrawing groups. The operationally simple and mild is performed at ambient temperature exhibits tolerance a variety functional

Textbook revision: Allylboronic acids, which are easily prepared from allylic alcohols, react readily and selectively with ketones without Lewis acid catalysts.

Abstract The catalytic asymmetric allylboration of cyclic imines with γ,γ‐disubstituted allylboronic acids provides products adjacent stereocenters in high yield and stereoselectivity. Various electrophiles, including 3,4‐dihydroisoquinolines indoles, were prenylated a fully stereodivergent fashion by switching the E / Z geometry allylboronate and/or enantiomer BINOL catalyst. 3‐Methylindole provided three stereoselectivity one synthetic operation.

Abstract A regioselective, nickel‐catalyzed photoredox allylation of secondary, benzyl, and α‐alkoxy radical precursors is disclosed. Through this manifold, a variety linear allylic alcohols allylated monosaccharides are accessible in high yields under mild reaction conditions. Quantum mechanical calculations [DFT DLPNO‐CCSD(T)] support the mechanistic hypothesis Ni 0 to II oxidative addition pathway followed by inner‐sphere allylation.

A redox-neutral alkyl Petasis reaction has been developed that proceeds via photoredox catalysis. diverse set of primary, secondary, and tertiary alkyltrifluoroborates participate effectively in this through a single-electron transfer mechanism, contrast to the traditional two-electron reaction, which accommodates only unsaturated boronic acids. This protocol is ideal diversify benzyl-type glyoxalate-derived aldehydes, anilines, toward rapid assembly libraries higher molecular complexity...

Abstract The base‐catalyzed allylic borylation of tertiary alcohols allows the synthesis 1,1‐disubstituted allyl boronates, in moderate to high yield. unexpected tandem performance Lewis acid–base adduct, [Hbase] + [MeO‐B 2 pin ] − favored formation 1,2,3‐triborylated species from and 1‐propargylic cyclohexanol at 90 °C.

Direct allylboration of various acyclic and cyclic aldimine, ketimine indole substrates was performed using allylboronic acids.

Pd-catalyzed allylic C-H trifluoroacetoxylation of substituted alkenes was performed using PhI(OCOCF(3))(2) as the oxidant and acyloxy source. Trifluoroacetoxylation monosubstituted cyclopentenes cyclohexenes proceeds with excellent regio- diastereoselectivity. Studies one possible (η(3)-allyl)Pd(II) intermediates suggest that reaction via stereoselective formation Pd(IV) subsequent stereo- regioselective reductive elimination product.

An operationally simple, mild, redox-neutral method for the cross-coupling of α-hydroxyalkyltrifluoroborates is reported. Utilizing an Ir photocatalyst, α-hydroxyalkyl radicals are generated from single-electron oxidation trifluoroborates, and these subsequently engaged in a nickel-catalyzed C–C bond-forming reaction with aryl halides. The process highly selective, functional group tolerant, step economical, which allows direct synthesis secondary benzylic alcohol motifs.

Abstract The catalytic asymmetric allylboration of cyclic imines with γ,γ‐disubstituted allylboronic acids provides products adjacent stereocenters in high yield and stereoselectivity. Various electrophiles, including 3,4‐dihydroisoquinolines indoles, were prenylated a fully stereodivergent fashion by switching the E / Z geometry allylboronate and/or enantiomer BINOL catalyst. 3‐Methylindole provided three stereoselectivity one synthetic operation.

The direct reductive amination of aromatic aldehydes has been realized using a photocatalyst under visible light irradiation. single electron oxidation an in situ formed aminal species generates the putative α-amino radical that eventually delivers product. This method is operationally simple, highly selective, and functional group tolerant, which allows synthesis benzylic amines by unique mechanistic pathway.

Allylboronic acids directly react with acyl hydrazones, affording homoallylic amine derivatives. The reaction proceeds very high syn selectivity, which is the opposite of stereochemistry observed for allylboration imines. can be carried out both aromatic and aliphatic hydrazones. Based on our studies excellent explained by chelation control hydrazone B(OH)2 moiety.

Abstract A regioselective, nickel‐catalyzed photoredox allylation of secondary, benzyl, and α‐alkoxy radical precursors is disclosed. Through this manifold, a variety linear allylic alcohols allylated monosaccharides are accessible in high yields under mild reaction conditions. Quantum mechanical calculations [DFT DLPNO‐CCSD(T)] support the mechanistic hypothesis Ni 0 to II oxidative addition pathway followed by inner‐sphere allylation.

Steht so nicht im Lehrbuch: Allylboronsäuren sind leicht ausgehend von Allylalkoholen erhältlich und reagieren ohne Zusatz Lewis-Säure-Katalysatoren bereitwillig selektiv mit Ketonen. Allyl boronates are very important reagents in advanced organic synthesis for the allylation of carbonyl compounds1 and cross-coupling2 reactions. A practically unrivalled property allylboronates is their highly regio- stereoselective addition to compounds afford homoallylic alcohols.1a–1d, 3 This high...

Allylboronic acids readily react with a broad variety of ketones, affording homoallylic alcohols adjacent quaternary and tertiary stereocenters. The reaction proceeds very high anti stereoselectivity even if the substituents keto group have similar size. α-Keto syn probably due to formation acyl boronate intermediates. allylation reactions proceed without added acids/bases under mild conditions. Because this, many functionalities are tolerated in situ generated allylboronic acids.

Abstract The base‐catalyzed allylic borylation of tertiary alcohols allows the synthesis 1,1‐disubstituted allyl boronates, in moderate to high yield. unexpected tandem performance Lewis acid–base adduct, [Hbase] + [MeO‐B 2 pin ] − favored formation 1,2,3‐triborylated species from and 1‐propargylic cyclohexanol at 90 °C.

Abstract Allylic alcohols having two adjacent quarternary stereocenters can be prepared from γ‐disubstituted prenyl‐type boronic acids and ketones in the presence of BINOL‐derivatives as catalyst.

Abstract Unless otherwise mentioned the products are isolated as single diastereomers.