Origin of Diastereoselection in the Hydrosilylation of Chiral <i>N</i>‐Acyliminium Intermediates Derived from Pyroglutamic Acid

Oba, Makoto; Koguchi, Shinichi; Nishiyama, Kozaburo; Kaneno, Daisuke; Tomoda, Shuji

doi:10.1002/anie.200353366

Cited by 11 publications

(2 citation statements)

References 25 publications

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“…The rate‐determining rearomatization step was found to be important for the selective formation of syn product 40 . However, the sidechain‐substituent‐dependent syn / anti selectivity in the hydrosilylation reaction of related cyclic iminium intermediates was explored by Oba, Nishiyama and Tomoda et al25…”

Section: Ch Arylationmentioning

confidence: 99%

Classical-Reaction-Driven Stereo- and Regioselective C(sp³)-H Functionalization of Aliphatic Amines

Mahato

Jana

2016

The Chemical Record

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A large variety of synthetic methods have been developed for the synthesis of functionalized aliphatic amines because of their broad spectrum of application. Metallic reagents/catalysts and/or toxic oxidants are involved in most of the cases. Direct CH functionalization of aliphatic amines via their classical condensation reactions with suitable carbonyl compounds is advantageous because this method avoids hazardous metallic reagents, toxic oxidants and pre-activation/pre-functionalization step(s). In this account, the concept of direct CH functionalization of aliphatic amines based on the classical condensation-isomerization-addition (CIA) strategy followed by recent contributions from our ongoing research in the field along with relevant examples from other groups are described. Successes in stereo- and regioselective CC and CO bond formation via direct α- as well as β-C(sp(3) )-H functionalization are discussed.

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Section: Ch Arylationmentioning

confidence: 99%

Classical-Reaction-Driven Stereo- and Regioselective C(sp³)-H Functionalization of Aliphatic Amines

Mahato

Jana

2016

The Chemical Record

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“…It has been reported that Lewis acid-promoted allylation of 16a with allyltrimethylsilane occurs stereoselectively from the same face as the methoxycarbonyl group to give cis - 17a . The allylation using a model substrate 16b gave a 7 R -isomer 17b , exclusively.…”

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confidence: 99%

Total Synthesis of (−)-Kaitocephalin

et al. 2005

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[reaction: see text] Total synthesis of the potent AMPA/KA receptor antagonist (-)-kaitocephalin (1) and its three diastereomers has been accomplished. The synthesis features strictly substrate-controlled operations to alpha-formylglutamate 3 starting with alpha-hydroxymethylglutamate 4. The requisite 2R,3S,7R-stereocenters were efficiently constructed by manipulation of stereoselective reactions: dihydroxylation of 7 followed by azide substitution of the corresponding thionocarbonate 10 and Cu-mediated allylation of an acyliminium ion 21. All of the protecting groups in 26 were removed simultaneously by AlCl3/Me2S to give 1.

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Regio‐ and Diastereoselective and Enantiospecific Metal‐Free C(sp³)H Arylation: Facile Access to Optically Active 5‐Aryl 2,5‐Disubstituted Pyrrolidines

Haldar

Roy

Maity

et al. 2015

Chemistry A European J

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Optically active 5-aryl 2,5-disubstituted pyrrolidines are the principal structural moiety of many bioactive compounds including natural products and catalysts for asymmetric synthesis. A highly regio- and diastereoselective and enantiospecific method for direct C-H arylation of aliphatic amine has been developed. Structurally diverse enantiopure arylated pyrrolidines were synthesized from commercially available starting materials, through a single-step three-component reaction under metal- and oxidant-free conditions. Furthermore, the complex analogous structure of CCK antagonist RP 66803 and angiotensin-converting enzyme inhibitors was easily constructed using the synthesized arylated pyrrolidine derivative. Detailed theoretical calculations (M06-2X/TZVPP/SMD//M06-2X/6-31+G(d,p) level) were also carried to investigate the mechanism and high level of stereocontrol involved in this direct sp(3) C-H arylation reaction. Preference for a given regio- and stereoselectivity in the arylated product can be explained through elucidation of the mechanism for dehydration, generating azomethine ylide, and for the final re-aromatization step. The calculated energies reveals that the re-aromatization step is essentially rate determining, accompanying an activation barrier of Δ(≠) G=25.6 kcal mol(-1) .

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Origin of Diastereoselection in the Hydrosilylation of Chiral N‐Acyliminium Intermediates Derived from Pyroglutamic Acid

Cited by 11 publications

References 25 publications

Classical-Reaction-Driven Stereo- and Regioselective C(sp³)-H Functionalization of Aliphatic Amines

Classical-Reaction-Driven Stereo- and Regioselective C(sp³)-H Functionalization of Aliphatic Amines

Total Synthesis of (−)-Kaitocephalin

Regio‐ and Diastereoselective and Enantiospecific Metal‐Free C(sp³)H Arylation: Facile Access to Optically Active 5‐Aryl 2,5‐Disubstituted Pyrrolidines

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Origin of Diastereoselection in the Hydrosilylation of Chiral N‐Acyliminium Intermediates Derived from Pyroglutamic Acid

Cited by 11 publications

References 25 publications

Classical-Reaction-Driven Stereo- and Regioselective C(sp3)-H Functionalization of Aliphatic Amines

Classical-Reaction-Driven Stereo- and Regioselective C(sp3)-H Functionalization of Aliphatic Amines

Total Synthesis of (−)-Kaitocephalin

Regio‐ and Diastereoselective and Enantiospecific Metal‐Free C(sp3)H Arylation: Facile Access to Optically Active 5‐Aryl 2,5‐Disubstituted Pyrrolidines

Contact Info

Product

Resources

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Classical-Reaction-Driven Stereo- and Regioselective C(sp³)-H Functionalization of Aliphatic Amines

Classical-Reaction-Driven Stereo- and Regioselective C(sp³)-H Functionalization of Aliphatic Amines

Regio‐ and Diastereoselective and Enantiospecific Metal‐Free C(sp³)H Arylation: Facile Access to Optically Active 5‐Aryl 2,5‐Disubstituted Pyrrolidines