Catalytic Enantioselective Desymmetrisation as a Tool for the Synthesis of Hodgkinsine and Hodgkinsine B

Snell, Robert H.; Durbin, Matthew J.; Woodward, Robert L.; Willis, Michael C.

doi:10.1002/chem.201203150

Cited by 27 publications

(15 citation statements)

References 90 publications

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“…In the synthesis of the fungal alkaloid (−)-ardeemin (from Aspergillus fischeri), the pyrroloindole fragment was accessed by cyclopropanation of N -methylindole in a tryptophan-derived precursor, which directly cyclized to the pyrroloindole ring system presumably via an iminium ion intermediate . Oxidative dimerization of tryptamine derivatives with [bis(trifluoroacetoxy)iodo]benzene, which can be viewed as a mechanistically related process, has been used in the synthesis of dimeric pyrroloindole alkaloids meso -chimonanthine, hodgkinsine, and hodgkinsine B . Another oxidative coupling of an indole substrate that potentially implicates iminium ions in the construction of the pyrroloindole subunit is featured in the synthesis of (−)-vincorine (Figure ).…”

Section: Addition To the Carbon–nitrogen Double Bondmentioning

confidence: 99%

Cutting-Edge and Time-Honored Strategies for Stereoselective Construction of C–N Bonds in Total Synthesis

et al. 2016

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The main objective of this review is to provide a comprehensive survey of methods used for stereoselective construction of carbon-nitrogen bonds during the total synthesis of nitrogen-containing natural products that have appeared in the literature since 2000. The material is organized by specific reaction in order of decreasing number of applications in natural product synthesis. About 800 total syntheses of natural products with stereogenic carbon-nitrogen bonds described since 2000 have been reviewed.

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Section: Addition To the Carbon–nitrogen Double Bondmentioning

confidence: 99%

Cutting-Edge and Time-Honored Strategies for Stereoselective Construction of C–N Bonds in Total Synthesis

et al. 2016

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“…All solvents were obtained from commercial sources and were purified according to standard procedures. Acids 1 were prepared according to known procedures. , Substrates 5 were commercially available and were used without further purification. Purification of the products was accomplished by flash chromatography using silica gel (200–300 mesh).…”

Section: Methodsmentioning

confidence: 99%

β-Functionalization of Indolin-2-one-Derived Aliphatic Acids for the Divergent Synthesis of Spirooxindole γ-Butyrolactones

et al. 2017

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β-Functionalization of indolin-2-one-derived aliphatic acids has been applied in formal [3 + 2] annualtions for catalyst-free and divergent synthesis of two series of structurally interesting 3,3'-spirooxindole γ-butyrolactones that may be attractive for potential drug discovery. These findings also pave the way for further diversity-oriented synthesis of spirooxindoles starting from indolin-2-one-derived aliphatic acids or their derivatives.

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“…The desymmetrization methodology has been used in a variety of synthetic venues including natural product total synthesis via formation of a chiral axis 73 and in the development of molecular rotors. 74 In a report by Sasai in 2009, an enantioselective double N-arylation was employed to access C2-symmetric spiranes from malonamides (Scheme 28).…”

Section: Scheme 27 -Synthesis Of Atropisomeric 2-aryl-4-quinolinones Via Tandem Amination 153 Desymmetrization Via N-arylationmentioning

confidence: 99%

Synthesis and Application of Chiral Palladium-Phosphane Precatalyst in Enantioselective C-N Cross-Coupling

Wright¹

2021

Preprint

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The various strategies and reaction conditions towards the synthesis of benzene-, naphthalene-, and phenanthrene-based dicyclohexylbiaryl phosphanes are presented. A chiral third generation Buchwald-type precatalyst has been synthesized, employing the non-commercially available ligand, (R)-dicyclohexyl(2'-methoxy-[1,1'-binaphth-2-yl])phosphane, (R)-Cy2MOP, and a dimeric methanesulfonate-bridged palladacycle based on a 2-aminobiphenyl scaffold. Application of the palladacyclic precatalyst in an enantioselective variant of the BuchwaldHartwig reaction is demonstrated in the desymmetrization of prochiral α-(2-bromobenzyl)malonamides via intramolecular N-arylation. The scope of the catalysis in the presence of the precatalyst has been investigated with efforts towards optimizing yields, catalyst loading, and enantioselectivities. Attempts towards the isolation of a potential reaction intermediate in the form of a stable amido-bound palladium complex are discussed. Finally, strategies towards gaining mechanistic insight on the origin of the enantiomeric excess are discussed.

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Catalytic Enantioselective Desymmetrisation as a Tool for the Synthesis of Hodgkinsine and Hodgkinsine B

Cited by 27 publications

References 90 publications

Cutting-Edge and Time-Honored Strategies for Stereoselective Construction of C–N Bonds in Total Synthesis

Cutting-Edge and Time-Honored Strategies for Stereoselective Construction of C–N Bonds in Total Synthesis

β-Functionalization of Indolin-2-one-Derived Aliphatic Acids for the Divergent Synthesis of Spirooxindole γ-Butyrolactones

Synthesis and Application of Chiral Palladium-Phosphane Precatalyst in Enantioselective C-N Cross-Coupling

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