Axially chiral bidentate ligands in asymmetric catalysis

McCarthy, Marie; Guiry, Patrick J.

doi:10.1016/s0040-4020(01)00087-4

Cited by 405 publications

(148 citation statements)

References 184 publications

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“…Since the Heck oxyarylation reaction of 7-benzyloxy-2H-chromene (13) and 2-iodophenol (14) has been already performed by two of us using 1,2-bis(diphenylphosphino)ethane (dppe) as ligand and Ag 2 CO 3 as base 5 (Scheme 1) it could be expected that the change of 1,2-bis(diphenylphosphino)ethane to optically active phosphine ligands could result in optically active 15. (19) 19 were selected for testing, based on literature data.…”

Section: Resultsmentioning

confidence: 99%

“…Although intermolecular Heck oxyarylation is widely used in the synthesis of racemic pterocarpans [7][8][9][10] , in contrast to the conventional Heck reaction [11][12][13][14] , its mechanism is not fully understood. It presumably proceeds also via the generation of active Pd(0), oxidative addition of the aryl iodide to Pd(0), followed by regioselective syn-addition of 6 to 7 and palladium displacement by the phenolic oxygen whose details are not known ( Figure 1).…”

Section: Introductionmentioning

confidence: 99%

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Further insight into the mechanism of Heck oxyarylation in the presence of chiral ligands

Kiss¹,

Kurtán²,

Antus³

et al. 2003

Arkivoc

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The Heck oxyarylation reaction to 3-benzyloxypterocarpan (15) has been studied in the presence of chiral phosphine ligands, a chiral ionic liquid and (+)-α-pinene. The observed small selectivities suggest that this reaction takes place through parallel pathways and the main pathway involves an achiral intermediate 11 where the chirality introduced by the chiral ligands is lost. Although practical asymmetric Heck oxyarylation to chiral pterocarpans could not be achieved, a convenient Heck-oxyarylation synthesis of rac-15 with (+)-α-pinene as ligand gave the highest yield reported to this type of reactions.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Further insight into the mechanism of Heck oxyarylation in the presence of chiral ligands

Kiss¹,

Kurtán²,

Antus³

et al. 2003

Arkivoc

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“…BINAPs [2,2'-bis(diphenylphosphino)-1,1'-binaphthyls] are prominent scaffolds and considered "privileged" ligands [9,10]. The related BINAP-based, aminophosphine ligands (N,P bidentate instead of P,P-bidentate) emerged almost two decades ago and appeared in a wide range of asymmetric applications, such as allylic alkylation, cross-coupling, and hydrogenation reactions [11][12][13][14].…”

Section: Open Accessmentioning

confidence: 99%

Synthesis of New BINAP-Based Aminophosphines and Their 31P-NMR Spectroscopy

et al. 2013

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BINAP aminophosphines are prevalent N,P-bidentate, chiral ligands for asymmetric catalysis. While modification via the BINAP-nitrogen linkage is well explored and has provided a diverse body of derivatives, modification of the other substituents of the phosphorous center is another avenue in generating new congeners of this important class of chiral ligands. Herein reported are new BINAP aryl aminophosphines with electron rich or deficient substituents on the aryl rings. This scalable synthesis converted readily available starting material, (S)-BINOL, to a key intermediate (S)-NOBIN, from which the final chiral aminophosphines were prepared via a palladium-catalyzed, phosphonylation reaction. The aryl substituents are able to modify the electronic properties of the phosphorous center as indicated by the range of 31 P-NMR shifts of these new ligands. A computational analysis was performed to linearly quantitate contributions to the 31 P-NMR shifts from both resonance and field effects of the substituents. This correlation may be useful for designing and preparing other related aminophosphines with varying ligand properties.

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“…Among the well-known methods for asymmetric synthesis, catalysis gained an ever-growing success since it presents many advantages with respect to the traditional wasteful stoichiometric methods (chiral auxiliaries, chiral-pool approaches): the catalyst is used at low or very low loading, the starting material does not need to come from the chiral pool, and the synthesis does not require extra steps for the installation and removal of a chiral auxiliary. For these reasons, the chiral catalyst approach has been extensively exploited in the last decades and many review papers have been written on this topic [6][7][8][9]. Furthermore, the chemistry community has strongly believed in the potential of metal-catalysed transformation, which therefore has been broadly explored through the years leading to remarkable results in the stereoselective synthesis [10,11].…”

Section: Introduction Asymmetric Synthesis: the Query And The Offermentioning

confidence: 99%

Organocatalysts for enantioselective synthesis of fine chemicals: definitions, trends and developments

Federsel¹

2014

ScienceOpen Research

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Organocatalysis, that is the use of small organic molecules to catalyse organic transformations, has been included among the most successful concepts in asymmetric catalysis and it has been used for the enantioselective construction of C-C, C-N, C-O, C-S, C-P, and C-halide bonds. Since the seminal works in early 2000, the scientific community has been paying an ever-growing attention to the use of organocatalysts for the synthesis, with high yields and remarkable stereoselectivities, of optically active fine chemicals of interest for the pharmaceutical industry. A brief overview is here presented about the two main classes of substrate activation by the catalyst: covalent organocatalysis and non-covalent organocatalysis, with a more stringent focus on some recent outcomes in the field of the latter and of hydrogen-bond-based catalysis. Finally, some successful examples of heterogenisation of organocatalysts are also discussed, in the view of a potential industrial exploitation.

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Axially chiral bidentate ligands in asymmetric catalysis

Cited by 405 publications

References 184 publications

Further insight into the mechanism of Heck oxyarylation in the presence of chiral ligands

Further insight into the mechanism of Heck oxyarylation in the presence of chiral ligands

Synthesis of New BINAP-Based Aminophosphines and Their 31P-NMR Spectroscopy

Organocatalysts for enantioselective synthesis of fine chemicals: definitions, trends and developments

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