Combined Metalation-Palladium-Catalyzed Cross Coupling Strategies. A Formal Synthesis of the Marine Alkaloid Amphimedine

Guillier, F.; Nivoliers, F.; Godard, Alain; Marsais, Francis; Quéguiner, G.; Siddiqui, M. Arshad; Snieckus, Victor

doi:10.1021/jo00107a004

Cited by 73 publications

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“…1) held promise as a tunable and easily constructed acyltransfer catalyst template capable of operating via an induced-fit mechanism. 31 The synthesis of 2 was straightforward: conversion of 3 32 to its acid-chloride followed by coupling with (S)-phenylalaninolderived 4 33 gave chloropyridine 5, which could be converted to 2 via a nucleophilic aromatic substitution reaction with excess pyrrolidine (Scheme 1). An immediate cause for concern was the presence of two rotameric species in a ca.…”

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confidence: 99%

Asymmetric acyl-transfer promoted by readily assembled chiral 4-N,N-dialkylaminopyridine derivatives

et al. 2006

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The development of a new class of chiral 4-N,N-dialkylaminopyridine acyl-transfer catalysts capable of exploiting both van der Waals (p) and H-bonding interactions to allow remote chiral information to stereochemically control the kinetic resolution of sec-alcohols with moderate to excellent selectivity (s = 6-30). Catalysts derived from (S)-a,a-diarylprolinol are considerably superior to analogues devoid of a tertiary hydroxyl moiety and possess high activity and selectivity across a broad range of substrates.Asymmetric organocatalysis has recently been propelled from relative obscurity to the forefront of contemporary organic chemistry research and is fast-becoming a key strategy in enantioselective synthesis. 1, 2 An important facet of this broad domain is the asymmetric nonenzymatic 3 catalysis of acyl-transfer by chiral organic nucleophiles such as tertiary amines, 4-7 phosphines, 8 N-heterocyclic carbenes 9,10 and secondary alcohols. 11 Although it has been over a century since the discovery of pyridine-promoted alcohol acylation, 12 the design of efficient and selective chiral pyridine-based catalysts for these reactions is a young field less than 10 years old. The desymmetrisation of the 'hypernucleophilic' achiral catalyst 4-N,N-dimethylaminopyridine (DMAP) 13,14 via one of three general strategies, (the introduction of 'planar chirality' either 2,3-pyridofused 15 or installed at the C-3-position of the pyridine ring, 16 the use of axially chiral substituents at C-3 17 or the installation of tetrahedral chirality at either C-4, 18-23 or C-3, 24-27 ) has proven a particularly productive approach which has given rise to a number of highly selective chiral catalysts for the kinetic resolution (KR) of sec-alcohols and other asymmetric acyl-transfer processes. 15,27, 28 The design of such systems is complicated by an activityselectivity conundrum: i.e. to maximise the effectiveness of catalyst stereochemical information it is desirable to install chiral groups as close to the nucleophilic ring nitrogen as possible, however, bulky substituents in the vicinity of the same strongly attenuate catalyst activity. 14,17c,29 A successful (i.e. active and selective) catalyst design must necessarily embody a compromise between these opposing constraints.One appealing solution to this problem (inspired by enzymatic systems) is the design of promoters capable of operating by an 'induced-fit' mechanism, in which the catalyst undergoes a a Centre for Synthesis and Chemical Biology, School of Chemistry, University of Dublin, Trinity College, Dublin 2, Ireland. E-mail: connons@tcd.ie; Fax: +353 1 6712826; Tel: +353 1 6081306 b School of Chemistry, University of Dublin, Trinity College, Dublin 2, Ireland † Electronic supplementary information (ESI) available: General experimental procedures and details, characterisation data for the synthesis of catalysts 14 and 15, 1 H and 13 C NMR spectra for 6 and 7 (and their precursors), X-ray crystal structure data for 6-Bn, atomic coordinates from the DFT calculations and CSP...

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confidence: 99%

Asymmetric acyl-transfer promoted by readily assembled chiral 4-N,N-dialkylaminopyridine derivatives

et al. 2006

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“…Thus, 4-bromonicotinate 157 (Scheme 14.32) and the ortho-N-Boc-aminophenylboronic acid 158, both derived by DoM chemistry, undergo smooth cross-coupling with concomitant lactamization to afford 159 in good yields. Alternatively, the cross-coupling of the bromonicotinate Noxide 160 with the same boronic acid 158 provides the analogous tricyclic 161, which, upon deoxygenation, leads to the same benzonaphthyridinone 159 [148]. afforded the azabiaryl 164 in modest yields.…”

Section: The Suzuki-miyaura Cross-couplingmentioning

confidence: 99%

“…Cross-coupling of ortho-iodoaniline 162 with the 4-(9-BBN)-nicotinamide 163, obtained by an appropriate DoM procedure, Scheme 14.32 Marine alkaloids. The DoM-Suzuki-Miyaura strategy for a key benzo[c][6,7]naphthyridinone moiety 161[148].…”

mentioning

confidence: 99%

The Directed Ortho Metallation (DoM)–Cross‐Coupling Nexus. Synthetic Methodology for the Formation of Aryl–Aryl and Aryl–Heteroatom–Aryl Bonds

Snieckus¹,

Anctil²

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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“…1) held promise as a tunable and easily constructed acyltransfer catalyst template capable of operating via an induced-fit mechanism. The synthesis of 2 was straightforward: conversion of 3 32 to its acid-chloride followed by coupling with (S)-phenylalaninolderived 4 33 gave chloropyridine 5, which could be converted to 2 via a nucleophilic aromatic substitution reaction with excess pyrrolidine (Scheme 1). An immediate cause for concern was the presence of two rotameric species in a ca.…”

Section: 2728mentioning

confidence: 99%

Asymmetric Acyl Transfer Promoted by Readily Assembled Chiral 4‐N,N‐Dialkylaminopyridine Derivatives.

Dálaigh¹,

Hynes²,

O’Brien³

et al. 2006

ChemInform

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The development of a new class of chiral 4-N,N-dialkylaminopyridine acyl-transfer catalysts capable of exploiting both van der Waals (p) and H-bonding interactions to allow remote chiral information to stereochemically control the kinetic resolution of sec-alcohols with moderate to excellent selectivity (s = 6-30). Catalysts derived from (S)-a,a-diarylprolinol are considerably superior to analogues devoid of a tertiary hydroxyl moiety and possess high activity and selectivity across a broad range of substrates.Asymmetric organocatalysis has recently been propelled from relative obscurity to the forefront of contemporary organic chemistry research and is fast-becoming a key strategy in enantioselective synthesis. 1,2An important facet of this broad domain is the asymmetric nonenzymatic 3 catalysis of acyl-transfer by chiral organic nucleophiles such as tertiary amines, 4-7 phosphines, 8 N-heterocyclic carbenes 9,10and secondary alcohols. 11 Although it has been over a century since the discovery of pyridine-promoted alcohol acylation, 12 the design of efficient and selective chiral pyridine-based catalysts for these reactions is a young field less than 10 years old. The desymmetrisation of the 'hypernucleophilic' achiral catalyst 4-N,N-dimethylaminopyridine (DMAP) 13,14 via one of three general strategies, (the introduction of 'planar chirality' either 2,3-pyridofused 15 or installed at the C-3-position of the pyridine ring, 16 the use of axially chiral substituents at C-3 17 or the installation of tetrahedral chirality at either C-4, 18-23 or C-3, 24-27 ) has proven a particularly productive approach which has given rise to a number of highly selective chiral catalysts for the kinetic resolution (KR) of sec-alcohols and other asymmetric acyl-transfer processes. 15,27,28The design of such systems is complicated by an activityselectivity conundrum: i.e. to maximise the effectiveness of catalyst stereochemical information it is desirable to install chiral groups as close to the nucleophilic ring nitrogen as possible, however, bulky substituents in the vicinity of the same strongly attenuate catalyst activity.14,17c,29 A successful (i.e. active and selective) catalyst design must necessarily embody a compromise between these opposing constraints.One appealing solution to this problem (inspired by enzymatic systems) is the design of promoters capable of operating by an 'induced-fit' mechanism, in which the catalyst undergoes a 1 H and 13 C NMR spectra for 6 and 7 (and their precursors), X-ray crystal structure data for 6-Bn, atomic coordinates from the DFT calculations and CSP-HPLC data for all resolved alcohols. See DOI: 10.1039/b604632k conformational change upon acylation driven by intramolecular interaction between the catalyst's chiral substituents and the pyridinium cation moiety, thereby allowing remote chirality to exercise stereochemical control over the subsequent acylation event.18,27 In this regard, we were intrigued by a report from Yamada and Morita 30 demonstrating that the 3-substituted pyridine 1 exh...

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Combined Metalation-Palladium-Catalyzed Cross Coupling Strategies. A Formal Synthesis of the Marine Alkaloid Amphimedine

Cited by 73 publications

References 0 publications

Asymmetric acyl-transfer promoted by readily assembled chiral 4-N,N-dialkylaminopyridine derivatives

Asymmetric acyl-transfer promoted by readily assembled chiral 4-N,N-dialkylaminopyridine derivatives

The Directed Ortho Metallation (DoM)–Cross‐Coupling Nexus. Synthetic Methodology for the Formation of Aryl–Aryl and Aryl–Heteroatom–Aryl Bonds

Asymmetric Acyl Transfer Promoted by Readily Assembled Chiral 4‐N,N‐Dialkylaminopyridine Derivatives.

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