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

Mailyan, Artur K.; Eickhoff, John A.; Minakova, Anastasiia S.; Gu, Zhenhua; Lü, Ping; Zakarian, Armen

doi:10.1021/acs.chemrev.5b00712

Cited by 150 publications

(98 citation statements)

References 945 publications

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“…Amines bearing a fully‐substituted stereocenter in the α position find many applications in the pharmaceutical and agrochemical industry, as well as in catalysis . Commensurate with their importance and abundance, numerous methods have been developed for their preparation, among which a prominent approach exploits the enantioselective addition of carbanion equivalents to imines derived from prochiral ketones . Ketimines are much more challenging electrophiles than their aldimine counterparts, due to their lower electrophilicity and the more difficult enantiodiscrimination between the two prochiral faces ,.…”

Section: Methodsmentioning

confidence: 99%

Catalytic Enantio‐ and Diastereoselective Mannich Addition of TosMIC to Ketimines

Franchino

Chapman

Funes‐Ardoiz

et al. 2018

Chemistry A European J

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Chiral amines bearing a stereocenter in the α position are ubiquitous compounds with many applications in the pharmaceutical and agrochemical sectors, as well as in catalysis. Catalytic asymmetric Mannich additions represent a valuable method to access such compounds in enantioenriched form. This work reports the first enantio‐ and diastereoselective addition of commercially available p‐toluenesulfonylmethyl isocyanide (TosMIC) to ketimines, affording 2‐imidazolines bearing two contiguous stereocenters, one of which is fully‐substituted, with high yields and excellent stereocontrol. The reaction, catalyzed by silver oxide and a dihydroquinine‐derived N,P‐ligand, is broad in scope, operationally simple, and scalable. Derivatization of the products provides enantioenriched vicinal diamines, precursors to NHC ligands and sp3‐rich heterocyclic scaffolds. Computations are used to understand catalysis and rationalize stereoselectivity.

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Section: Methodsmentioning

confidence: 99%

Catalytic Enantio‐ and Diastereoselective Mannich Addition of TosMIC to Ketimines

Franchino

Chapman

Funes‐Ardoiz

et al. 2018

Chemistry A European J

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“…Carbon-nitrogen (CÀ N) bonds exist in a large number of organic compounds containing naturally occurring and pharmaceutically relevant molecules, so the highly efficient construction of the CÀ N bonds is one of most significant research topics in the synthetic community. [1] To date, many useful methods have been developed such as classic substitution and addition reactions of amines or amides. Among them, the utilization of nitrogen-containing heterocycles could achieve synthesis of the interesting N-heterocycle derivatives by the formation of the CÀ N bonds.…”

Section: Introductionmentioning

confidence: 99%

Gold‐Catalyzed Reaction of 2H‐Tetrazoles with Alkynes: Efficient Route to N‐Alkenylated Tetrazoles

et al. 2019

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A gold‐catalyzed reaction of 2H‐tetrazoles with alkynes was described for the efficient synthesis of a variety of N‐alkenylated tetrazole derivatives, including N‐1 and N‐2 vinyl functionalized products which are readily isolated by column chromatography. The reaction mechanism was proposed to be a nucleophilic addition process to the alkyne motif activated by gold catalyst. The reaction features mild reaction condition, simple operation and high yields.

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“…[15,16] As the N-substituted C(sp 3 )s tereocenters of 2a-d and 3 possess the same configuration, the radical acceptor 4 would also be applied to establish the C2''S configuration of 3 through C2''À C3'' bond formation from 6. [15,16] As the N-substituted C(sp 3 )s tereocenters of 2a-d and 3 possess the same configuration, the radical acceptor 4 would also be applied to establish the C2''S configuration of 3 through C2''À C3'' bond formation from 6.…”

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confidence: 99%

Unified Total Synthesis of Polyoxins J, L, and Fluorinated Analogues on the Basis of Decarbonylative Radical Coupling Reactions

Inoue

Fujino²,

Nagatomo³

et al. 2017

Angewandte Chemie

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Polyoxins J(1a)a nd L(1b)a re important nucleoside antibiotics.T he complex and densely functionalized dipeptide structures of 1a and 1b contain thymine and uracil nucleobases,r espectively.H erein we report the unified total synthesis of 1a, 1b,a nd their artificial analogues 1c and 1d with trifluorothymine and fluorouracil structures.D ecarbonylative radical coupling between a-alkoxyacyl tellurides and achiral glyoxylic oxime ether led to chemo-and stereoselective construction of the ribonucleoside a-amino acid structures of 1a-d without damaging the preinstalled nucleobases.The high applicability of the radical-based methodology was further demonstrated by preparation of the trihydroxynorvaline moiety of 1a-d.The two amino acid fragments were connected and elaborated into 1a-d (longest linear sequence:1 1steps). Compounds 1a and 1b assembled in this way exhibited potent activity against true fungi, while only 1d was active against Gram-positive bacteria. Scheme 1. A) Structures of the four polyoxins 1a-d and synthetic plan. B) Decarbonylative radical reaction of 7 with achiral oxime 8 (Ref. [11]). Bn = benzyl, TBS = tert-butyldimethylsilyl. [*] H. Fujino, Dr.M.N agatomo,P rof. Dr.M .Inoue Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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

Cited by 150 publications

References 945 publications

Catalytic Enantio‐ and Diastereoselective Mannich Addition of TosMIC to Ketimines

Catalytic Enantio‐ and Diastereoselective Mannich Addition of TosMIC to Ketimines

Gold‐Catalyzed Reaction of 2H‐Tetrazoles with Alkynes: Efficient Route to N‐Alkenylated Tetrazoles

Unified Total Synthesis of Polyoxins J, L, and Fluorinated Analogues on the Basis of Decarbonylative Radical Coupling Reactions

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