Total Synthesis of <i>cis</i>‐Clavicipitic Acid from Asparagine via Ir‐Catalyzed CH bond Activation as a Key Step

Tahara, Yu Ki; Ito, Mamoru; Kanyiva, Kyalo Stephen; Shibata, Takanori

doi:10.1002/chem.201502300

Cited by 34 publications

(24 citation statements)

References 57 publications

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“…69 Using an alkenyl ketone as the directing group, cyclization of 121 provided the desired indole product 122 in 79% yield, and from this key intermediate cis -clavicipitic acid was synthesized in only three steps.…”

Section: Ketonesmentioning

confidence: 99%

Transition-Metal-Catalyzed C–H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds

2016

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The transition metal-catalyzed addition of C–H bonds to carbonyls, imines and related polarized π-bonds has emerged as a particularly efficient and powerful approach for the construction of an incredibly diverse array of heteroatom substituted products. Readily available and stable inputs are typically employed, and reactions often proceed with very high functionality group compatibility and without the production of waste byproducts. Additionally, many transition metal-catalyzed C–H bond additions to polarized π-bonds occur within cascade reaction sequences to provide rapid access to a diverse array of different heterocyclic as well as carbocyclic products. This review highlights the diversity of transformations that have been achieved, catalysts that have been used, and types of products that have been prepared through the transition metal catalyzed addition of C–H bonds to carbonyls, imines and related polarized π-bonds.

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Section: Ketonesmentioning

confidence: 99%

Transition-Metal-Catalyzed C–H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds

2016

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“…45 Shibata’s work was based on the expectation that indole 80 could be readily converted into (−)- cis clavicipitic acid through an intramolecular reductive amination (Figure 10). The C-H activation/cyclodehydration reaction would be deployed on indole precursor 81 , which in turn could be obtained in a convergent manner from aniline 82 and amino acid 83 .…”

Section: Synthetic Approaches To Rearranged Clavine Alkaloids Covementioning

confidence: 99%

Total synthesis, biosynthesis and biological profiles of clavine alkaloids

McCabe

Wipf

2016

Org. Biomol. Chem.

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This review highlights noteworthy synthetic and biological aspects of the clavine subfamily of ergot alkaloids. Recent biosynthetic insights have laid the groundwork for a better understanding of the diverse biological pathways leading to these indole derivatives. Ergot alkaloids were among the first fungal-derived natural products identified, inspiring pharmaceutical applications in CNS disorders, migraine, infective diseases, and cancer. Pergolide, for example, is a semi-synthetic clavine alkaloid that has been used to treat Parkinson’s disease. Synthetic activities have been particularly valuable to facilitate access to rare members of the Clavine family and empower medicinal chemistry research. Improved molecular target identification tools and a better understanding of signaling pathways can now be deployed to further extend the biological and medical utility of Clavine alkaloids.

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“…In 2015, Shibata and co-workers reported the diastereoselective total synthesis of clavicipitic acid by using Ir-catalyzed CÀ Hb ond activation as ak ey step, startingf rom natural amino acid l-asparagine (106)( Scheme 19). [21] Protected l-aspartic acid (Cbz-Asp-OMe) 107 was synthesized according to the liter-Scheme17. To talsynthesis via a4 -iodotryptophan derivative.…”

Section: Simultaneous Constructiono Fi Ndole and 4-substituted Tryptomentioning

confidence: 99%

“…Various strategies have been developed for the total synthesis of clavicipitic acid. [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23] There are two key points in the reported strategies:1 )the synthesis of a3 ,4-disubstituted indole;2 )the construction of the azepinoindole skeleton. From the former point of view,a lmost all total synthetic routes went through 4-substituted gramine or 4-substitutedt ryptophan derivatives as key intermediates.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, Schemes 13 and 17-19 show the corrects tereochemistry. [16,18,20,21] Total Syntheses via 4-Substituted Gramine Derivatives 4-Substitued gramine derivatives have been used as key intermediates for the total synthesis of ergot alkaloids. [23] This chapter is divided into two sections by the starting materials:4substituted indole and 3-substitutedi ndolei ncluding gramine.…”

Section: Introductionmentioning

confidence: 99%

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