The directed synthesis of axially chiral ligands, reagents, catalysts, and natural products through the ‘lactone methodology’

Bringmann, Gerhard; Tasler, Stefan; Pfeifer, Robert‐Michael; Breuning, Matthias

doi:10.1016/s0022-328x(02)01819-3

Cited by 82 publications

(28 citation statements)

References 142 publications

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“…[71] Catalyst 1 was also found useful in biaryl synthesis by direct intramolecular aryl palladation (10% load) [72,73] and domino sequences using allylic alkylation/Heck couplings. [74] Rawal et al have described a novel anion-accelerated intramolecular cyclization of alkenyl bromides onto phenols using 1.…”

Section: Vittorio Farina ð3þmentioning

confidence: 99%

High‐Turnover Palladium Catalysts in Cross‐Coupling and Heck Chemistry: A Critical Overview

2004

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This review discusses the problems associated with developing high-turnover catalysts for the cross-coupling and Heck reactions. New developments in the area, principally constituted by palladacycles and coordinatively unsaturated Pd catalysts featuring bulky phosphanes of high donicity, are reviewed from a mechanistic and synthetic standpoint, and compared with more traditional catalysts obtained from conventional mono-and polydentate Nand P-based ligands, as well as Pd catalysts without strong ligands, such as Pd colloids or heterogeneous catalysts. Carbene ligands are also briefly presented. Whereas a single, most promising approach to highturnover Pd catalysis cannot presently be defined, it is clear that the new "PdL 1 " catalysts (where L 1 is a monodentate bulky P ligand of high donicity) represent the latest, most important development in Pd research, certainly from the standpoint of scope and probably also from the standpoint of efficiency. High turnovers with these catalysts have been described and their use will certainly increase in the next few years. The review ends with a brief discussion containing practical considerations on how to choose a high TON catalyst for a given Heck or cross-coupling reaction of interest.

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Section: Vittorio Farina ð3þmentioning

confidence: 99%

High‐Turnover Palladium Catalysts in Cross‐Coupling and Heck Chemistry: A Critical Overview

2004

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“…[9] The most popular methods include: intramolecular oxidative couplings in the presence of a metal oxide or via a biarylcuprate intermediate, [10] the intermolecular (Meyers) Grignard/oxazoline coupling, [11] and the asymmetric ring cleavage of configurationally unstable biaryl lactones (Bringmann lactone method). [12] In the past few years, interesting novel concepts have emerged to complete this synthetic arsenal, such as the asymmetric coupling of phenols or anilines with aryllead triacetates, [13] the enantioselective oxidative homocoupling of naphthols catalyzed by copper(i) and a chiral diamine, [14] as well as various types of stereoselective benzannulations. [15] Today, the Suzuki-Miyaura coupling is certainly the most widely used method for the construction of the biaryl bond due to its great versatility and relatively environmentally friendly nature.…”

Section: Introductionmentioning

confidence: 99%

The Asymmetric Suzuki Coupling Route to Axially Chiral Biaryls

Baudoin

2005

Eur J Org Chem

307

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Axially chiral biaryls are ubiquitous structural motifs in biologically active natural products or ligands for homogeneous catalysis. Their properties relate to the particular spatial arrangement of the two aromatic residues and therefore the control of their absolute configuration constitutes an issue of major importance. The asymmetric Suzuki–Miyaura coupling has recently emerged as an attractive alternative to standard methods for the control of biaryl axial chirality. Recent diastereo‐ and enantioselective approaches, as well as some applications in target‐oriented synthesis, are commented on in this microreview. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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“…[3] Quite recently,M iyaji, Asano,a nd Matsubara accomplished ac hiral-urea-catalyzed asymmetric synthesis of 1-arylisoquinolines N-oxides on the basis of the same strategy. [5] Among the methods which use preformed racemic biaryls as substrates, [6] thea symmetric ring-opening strategy, reported by Bringmann et al, [7] wherein biaryl lactones serve as as ubstrates,i sr eliable from ap ractical point of view,but it requires an excess amount of achiral nucleophile. [5] Among the methods which use preformed racemic biaryls as substrates, [6] thea symmetric ring-opening strategy, reported by Bringmann et al, [7] wherein biaryl lactones serve as as ubstrates,i sr eliable from ap ractical point of view,but it requires an excess amount of achiral nucleophile.…”

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confidence: 99%

“…[4] Cross-coupling at the 2-position of the binaphthyl skeleton is also aviable DKR strategy,but as lightly high temperature is required because of the moderate configurational stability of the starting materials. [5] Among the methods which use preformed racemic biaryls as substrates, [6] thea symmetric ring-opening strategy, reported by Bringmann et al, [7] wherein biaryl lactones serve as as ubstrates,i sr eliable from ap ractical point of view,but it requires an excess amount of achiral nucleophile. Its utility is demonstrated in several total syntheses of biologically active compounds.…”

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confidence: 99%

Enantiodivergent Atroposelective Synthesis of Chiral Biaryls by Asymmetric Transfer Hydrogenation: Chiral Phosphoric Acid Catalyzed Dynamic Kinetic Resolution

2016

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Reported herein is an enantiodivergent synthesis of chiral biaryls by a chiral phosphoric acid catalyzed asymmetric transfer hydrogenation reaction. Upon treatment of biaryl lactols with aromatic amines and a Hantzsch ester in the presence of chiral phosphoric acid, dynamic kinetic resolution (DKR) involving a reductive amination reaction proceeded smoothly to furnish both R and S isomers of chiral biaryls with excellent enantioselectivities by proper choice of hydroxyaniline derivative. This trend was observed in wide variety of substrates, and various chiral biphenyl and phenyl naphthyl adducts were synthesized with satisfactory enantioselectivities in enantiodivergent fashion. The enantiodivergent synthesis of synthetically challenging, chiral o-tetrasubstituted biaryls were also accomplished, and suggests high synthetic potential of the present method.

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The directed synthesis of axially chiral ligands, reagents, catalysts, and natural products through the ‘lactone methodology’

Cited by 82 publications

References 142 publications

High‐Turnover Palladium Catalysts in Cross‐Coupling and Heck Chemistry: A Critical Overview

High‐Turnover Palladium Catalysts in Cross‐Coupling and Heck Chemistry: A Critical Overview

The Asymmetric Suzuki Coupling Route to Axially Chiral Biaryls

Enantiodivergent Atroposelective Synthesis of Chiral Biaryls by Asymmetric Transfer Hydrogenation: Chiral Phosphoric Acid Catalyzed Dynamic Kinetic Resolution

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