Recoverable Resin-Supported Pyridylamide Ligand for Microwave-Accelerated Molybdenum-Catalyzed Asymmetric Allylic Alkylations:  Enantioselective Synthesis of Baclofen

Belda, Oscar; Lundgren, Stina; Moberg, Christina

doi:10.1021/ol034605m

Cited by 62 publications

(25 citation statements)

References 23 publications

(18 reference statements)

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“…[121] Other enantioselective reactions performed by microwave heating include asymmetric Heck reactions [122] and ruthenium-catalyzed asymmetric hydrogen transfer processes. [123] …”

Section: Asymmetric Allylic Alkylationsmentioning

confidence: 99%

Controlled Microwave Heating in Modern Organic Synthesis

2004

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Although fire is now rarely used in synthetic chemistry, it was not until Robert Bunsen invented the burner in 1855 that the energy from this heat source could be applied to a reaction vessel in a focused manner. The Bunsen burner was later superseded by the isomantle, oil bath, or hot plate as a source for applying heat to a chemical reaction. In the past few years, heating and driving chemical reactions by microwave energy has been an increasingly popular theme in the scientific community. This nonclassical heating technique is slowly moving from a laboratory curiosity to an established technique that is heavily used in both academia and industry. The efficiency of “microwave flash heating” in dramatically reducing reaction times (from days and hours to minutes and seconds) is just one of the many advantages. This Review highlights recent applications of controlled microwave heating in modern organic synthesis, and discusses some of the underlying phenomena and issues involved.

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“…[121] Other enantioselective reactions performed by microwave heating include asymmetric Heck reactions [122] and ruthenium-catalyzed asymmetric hydrogen transfer processes. [123] …”

Section: Asymmetric Allylic Alkylationsmentioning

confidence: 99%

Controlled Microwave Heating in Modern Organic Synthesis

2004

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“…A number of pseudo-C 2 -symmetric pyridylamides having only one substituted pyridine ring ( Figure 3) has also been prepared and used as models for the development of a pyridylamide ligand attached to a TentaGel resin. 17 These ligands also afforded the product with high regioand enantioselectivity (74:1-98:1 and 97-99% ee, eq 1). A trend similar to that noted for the C 2 -symmetric analogues was observed for the substituent-regioselectivity relationship.…”

Section: Molybdenum-catalyzed Asymmetric Allylic Alkylations Belda Anmentioning

confidence: 97%

Molybdenum-Catalyzed Asymmetric Allylic Alkylations

2003

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The highly regio- and enantioselective molybdenum-catalyzed allylic alkylation reaction has become a powerful synthetic tool during the past few years. This Account describes the achievements gained so far in the area, with special attention directed to the different chiral ligands that have been used for inducing chirality in the products, the range of allylic substrates and nucleophiles employed, mechanistic studies, and applications of the reaction in asymmetric syntheses.

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“…The obtained lactam could be transformed into (R)-baclofen hydrochloride (26) using the reported procedure. [56][57][58][59] 2.5. Asymmetric Allylic Alkylation of 2-Phenyl Cycloalkenyl Carbonates 60) There are many reports of asymmetric allylic substitution using simple cycloalkenyl alcohol derivatives as substrates.…”

Section: Asymmetric Allylic Alkylation Using Nitromethane As the Nuclmentioning

confidence: 99%

Transition Metal-Catalyzed Asymmetric Reactions Using P-Chirogenic Diaminophosphine Oxides: DIAPHOXs

Nemoto

2008

CHEMICAL & PHARMACEUTICAL BULLETIN

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This review describes the development of a new class of chiral phosphorus ligands: amino acid-derived Pchirogenic diaminophosphine oxides, DIAPHOXs, and their application to several transition metal-catalyzed asymmetric allylic substitution reactions. Pd-catalyzed asymmetric allylic alkylation with cyclic b b-keto esters as prochiral nucleophiles was initially examined using P-chirogenic diaminophosphine oxide 1a, resulting in highly enantioselective construction of quaternary stereocenters. Mechanistic investigations revealed that 1a is activated by N,O-bis(trimethylsilyl)acetamide-induced tautomerization to afford a trivalent diamidophosphite species 13, which functions as the actual ligand. Pd-catalyzed asymmetric allylic substitutions of both acyclic and cyclic substrates were also examined using various nucleophiles such as malonate derivatives, nitromethane, aliphatic amines, and aromatic amines, providing a variety of chiral compounds with good to excellent enantioselectivity. In addition, Ir-catalyzed asymmetric allylic amination and alkylation of terminal allylic carbonates were examined using structurally optimized P-chirogenic diaminophosphine oxides, and the corresponding branched products were obtained in a highly regio-and enantioselective manner. Furthermore, the developed catalytic asymmetric process was successfully applied to the catalytic enantioselective synthesis of biologically active compounds, (R)-preclamol, (R)-baclofen hydrochloride, and (؊)-paroxetine.

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Recoverable Resin-Supported Pyridylamide Ligand for Microwave-Accelerated Molybdenum-Catalyzed Asymmetric Allylic Alkylations: Enantioselective Synthesis of Baclofen

Cited by 62 publications

References 23 publications

Controlled Microwave Heating in Modern Organic Synthesis

Controlled Microwave Heating in Modern Organic Synthesis

Molybdenum-Catalyzed Asymmetric Allylic Alkylations

Transition Metal-Catalyzed Asymmetric Reactions Using P-Chirogenic Diaminophosphine Oxides: DIAPHOXs

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