It′s just a phase: The title reaction sequence of para-quinone methides (p-QMs) has been developed with malonates under phase-transfer catalysis. also offers an alternative route to asymmetric construction diarylmethine stereocenters in excellent enantioselectivities and high yields. As service our authors readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed may be re-organized for online delivery, but not copy-edited or typeset....

This minireview summarizes the recent advances in synthesis of allenes with catalytic asymmetric methods.

A highly enantioselective synthesis of trisubstituted allenes has been achieved through Cu(I)-catalyzed cross-coupling aryldiazoalkanes and terminal alkynes with chiral bisoxazoline ligands. Alkynyl migratory insertion Cu(I) carbene is proposed as the key step for construction axial chirality.

A novel DBU-mediated stereoselective spirocyclopropanation of para-quinone methides with sulfonium salts has been developed on the basis mode involving a 1,6-conjugate addition/intramolecular dearomatizing cyclization cascade. This reaction provides mild and effective method for assembly synthetically structurally interesting spirocyclopropanyl para-dienones. The feasibility enantioselective access to such functionalized para-dienones also explored by using axially chiral salt. Importantly,...

Palladium-catalyzed asymmetric formal [3 + 2] cycloaddition of vinyl cyclopropanes and aldimines or isatin-derived ketimines proceeded smoothly in the presence chiral phosphoramidite ligands. The corresponding highly functionalized optically enriched pyrrolidine spiro[pyrrolidin-3,2'-oxindole] derivatives are obtained up to 94% yield with 96% ee 7:1 dr.

This review describes recent developments in the asymmetric transformations of achiral cyclohexadienones, including enantioselective desymmetrization prochiral cyclohexadienones and kinetic resolution racemic cyclohexadienones.

Günstige Phase: Die Titelreaktionssequenz von para-Chinonmethiden (p-QMs) und Malonaten unter Phasentransferkatalyse bietet eine Alternative für die hoch enantioselektive Einführung Diarylmethin-Stereozentren; Produkte werden in hohen Ausbeuten erhalten. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed may be re-organized for online delivery, but not copy-edited or typeset. Technical support issues...

An unprecedented umpolung spirocyclopropanation reaction of p-quinone methides and α-keto carbonyls is described. Our strategy based on 1,6-conjugate addition intramolecular nucleophilic substitution offers a new method for effective access to series highly functionalized spirocyclohexadienonyl cyclopropanes having two vicinal quaternary carbons in ≤98% yield >20:1 dr. Significantly, cyclic acyclic topological structures as 1,1-dipole one-carbon synthons have distinct influence the...

A Lewis acid Sc(OTf)3-catalyzed annulation reaction of vinyl diazoacetates with in situ formed α,β-unsaturated imines for the preparation indole-fused tricyclic rings has been reported. This strategy involves a sequential addition/rebound addition process and an dedinitrogenation. protocol features low-cost catalysts, mild conditions, facilely prepared substrates.

For the first time, aromatization-driven alternating copolymerization of p -QM with isothiocyanates is explored under mild conditions.

A novel enantioselective [4 + 2] annulation of the allenoates having a unique positive ortho-effect with in situ generated ortho-quinone methides has been developed under catalysis Cinchona alkaloid. This chiral amine-catalyzed reaction provides an alternative route to asymmetric catalytic construction synthetically interesting, highly functionalized chromans good excellent enantioselectivities (up 97% ee).

The first copper hydride (CuH)-catalyzed asymmetric 1,6-conjugate reduction of p-quinone methides is reported. This protocol provides a new method to access variety triarylmethanes and 1,1,2-triarylethanes in good yields with excellent enantioselectivities broad functional group tolerance.

An unprecedented cycloaddition of vinyl diazo compounds with benzofuran-derived azadienes catalyzed by rarely independently used NaBArF4 has been established. Benzofuran-fused hydropyridines were constructed excellent yields and high diastereoselectivity via a Na+-catalyzed inverse-electron-demand aza-Diels-Alder reaction. Notably, this transformation also features good compatibility one-pot protocol to deliver the spiro[benzofuran-cyclopentene] skeleton, as well perfect atom economy simple...

To synthesize high molecular weight poly(phenolic ester) via a living ring-opening polymerization (ROP) of cyclic phenolic ester monomers remains critical challenge due to serious transesterification and back-biting reactions. Both bonds in monomer polymer chains are highly active, it is difficult so far distinguish them. In this work, an unprecedented selectively bifunctional catalytic system tetra-n-butylammonium chloride (TBACl) was discovered mediate the syntheses salicylic acid-based...

The scope and limitations of the acylation preformed lithium enolates by methyl cyanoformate have been explored further. In particular, proportion C-acylation products in sterically hindered substrates is significantly enhanced use diethyl ether as solvent, while diastereofacial selectivity reactions chiral found to be similar that observed for C-alkylations most cases. Exceptions may occur a consequence higher steric demand reagent, however.

Finding a common path: A synthetic strategy inspired by the proposed biogenesis of montanine-type alkaloids enabled concise asymmetric synthesis these compounds in divergent fashion on basis an unprecedented tandem oxidative dearomatization/intramolecular aza-Michael addition as key step. This bioinspired approach revealed chemical connection between cherylline- and (see scheme). As service to our authors readers, this journal provides supporting information supplied authors. Such materials...

The pain ends here: A novel synthetic strategy for the construction of (±)-morphine rings B and E was developed, in which SmI2-promoted reductive coupling/desulfurization tandem alcoholysis/oxa-Michael addition featured as key steps assembly C9C14 C5O bonds, respectively. Asymmetric also feasible enantiocontrolled synthesis morphine.

Herein, we report the Pd(0)-catalyzed intermolecular asymmetric dearomative [3 + 2] annulation of phenols with vinyl cyclopropanes via in situ generated ortho-quinone methide intermediates. A series highly functionalized spiro-[5,6] bicycles which bear three contiguous stereogenic centers including one all-carbon quaternary were obtained excellent stereoselectivities. Density functional theory (DFT) calculations indicate that reactions controlled by thermodynamics.

A chiral bifunctional Brønsted base-catalyzed enantioselective [3 + 2] cycloaddition of D–A cyclopropanes and azadienes is reported. The protocol features broad substrate scope, mild reaction conditions high functional group tolerance.

Asymmetric conjugate addition of PhMe₂SiBPin to a wide range <italic>N</italic>-heteroaryl alkenes proceeded in the presence copper catalyst coordinated with chiral phosphoramidite ligand afford useful β-silyl <italic>N</italic>-heteroarenes high yields and ees.