Direct Catalytic Asymmetric Aldol Reaction of an α‐Azido Amide

Weidner, Karin; Sun, Zhongdong; Kumagai, Naoya; Shibasaki, Masakatsu

doi:10.1002/ange.201501607

Cited by 24 publications

(5 citation statements)

References 60 publications

(21 reference statements)

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“…The authors also found that aromatic aldehydes without an ortho substituent gave only the syn ‐aldol products, irrespective of the chiral ligands used. Moreover, 2‐flourobezaldehyde failed to yield any product under the catalysis of mesitylcopper/ 140 . These results hinted that the steric effects at the ortho position are crucial for obtaining anti products.…”

Section: Metal Complex‐catalyzed Diastereodivergent Reactionsmentioning

confidence: 96%

“…Recently, Kumagai, Shibasaki, and co‐workers developed another diastereodivergent direct aldol reaction of α‐azido amide 176 and ortho ‐substituted aromatic aldehydes 175 for the synthesis of β‐hydroxy‐α‐azido amides 177 , employing co‐operative catalysis (Scheme ) . The use of different chiral ligands with mesitylcopper induced the diastereodivergence in the reaction.…”

Section: Metal Complex‐catalyzed Diastereodivergent Reactionsmentioning

confidence: 99%

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Advances in Asymmetric Diastereodivergent Catalysis

2017

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Because the biological and/or pharmacologicalp roperties of ag iven molecule often depend on the absolutea nd relative configurations of the stereogenic centers,d ifferent diastereomers may exhibit totally different biological and/or pharmacological activities.T herefore,f or compoundsc ontaining multiple stereogenic centers,t he stereoselective asymmetric synthesis of all of the individual diastereomers, preferably using ac atalytic method, is of great interest andi mportance in organic synthesis and drug discovery.I nt his context, the development of catalytic diastereodivergent methods is highly desirable,s incei tp rovides one of the most efficient ways to access multipled iastereomers from the same substrates.T he current review attemptst os umma-rize the developments in the field of asymmetric diastereodivergent catalysis. Scheme 5. Michaelr eactions for the synthesis of both syn-and anti-diastereomers. Scheme 6. Diastereodivergent tandem Michael-Michael reaction. Scheme 8. Diastereodivergent aldol reactionsofc ycloketones andaryl aldehydes. Scheme 9. l-Proline/guanidinium salt co-catalyzed diastereodivergent aldol reactions. Scheme 7. Diastereodivergent synthesis of 2,4-dinitro ester derivatives using bifunctional squaramidec atalysts. Scheme 11. Diastereodivergent synthesis of spirooxindole derivatives.Scheme 12. Diastereodivergent synthesis of bis(spirocyclic)oxindoles derivatives. Scheme 14. Diastereodivergent formal hydroaminination, hydrooxidation, and reductive Mannich reaction of enal 52. Scheme 15. Diastereodivergent alkylamination, diamination, and aminooxidation of enal 64. Scheme 16. Generation of diastereodivergence in the one-pot sequential cycle-specific catalysis. Scheme 17. Organocatalytic diastereodivergent synthesis of furan-fused carbocycles. Scheme 18. Accesstot he full matrixo fthe stereoisomers of the annulated furan. Scheme 19. Diastereodivergent cascade reaction towards chiral diamine derivatives. Scheme 23. Diastereodivergent synthesis of indolo[2,3-a]-, benzo[a]-, and thieno[3,2-a]quinolizidine skeletons. Scheme 24. Diastereodivergent [4+ +2] cycloaddition of cyclic enones with alkenyl-or alkynylmethylidenemalononitriles. Scheme 25. Diastereodivergent synthesis of cyclohexane derivativesu sing bifunctional squaramide catalysts. Scheme 26. Diastereodivergent synthesis of polyfuntionalized cyclohexanes using MDOs. Scheme 27. Enantioselectived iastereodivergentsynthesis of lycorane diastereomers using MDOs. Scheme 28. Diastereodivergent tandem hetero-Diels-Alder/oxa-Michael reaction catalyzed by MDOs. Scheme 29. Diastereodivergent approach towards dihydrobezofuran derivatives. Scheme 30. Diastereodivergent approach towards tetrahydrofuran derivatives. Scheme 31. Proposed transition states leading to cis-a nd trans-dihydrobenzofuran derivatives. Scheme 32. Adiastereodivergent[4 + +2] annulation of 16 and 127. Scheme 35. Diastereodivergent cycloaddition of azomethine ylides with C 60 . Scheme 36. Diastereodivergent synthesis of the four stereoisomers of the pyrrolidinoendofullerenes. S...

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Section: Metal Complex‐catalyzed Diastereodivergent Reactionsmentioning

confidence: 96%

Section: Metal Complex‐catalyzed Diastereodivergent Reactionsmentioning

confidence: 99%

Advances in Asymmetric Diastereodivergent Catalysis

2017

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“…In the latter case, metal-chiral phosphine catalyst systems have proven to be uniquely successful catalyst systems, as the diverse range of chiral bisphosphine, phosphoramidite, and P,N ligands available have enabled the development of a range of stereodivergent reactions. 38 39 40 41 42 43…”

Section: Mono-catalysismentioning

confidence: 99%

Stereodivergent Carbon–Carbon Bond-Forming Reactions

Healy

2024

Synthesis

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Stereodivergent catalysis has emerged as a compelling strategy for achieving stereochemical diversity in small-molecule library design and natural product synthesis. In this short review, key examples of pioneering catalytic carbon–carbon bond-forming transformations that provide access to all stereoisomers of a given product are presented. Current trends and future directions in the field are discussed, highlighting ongoing initiatives to enhance the efficiency and broaden the scope of stereodivergent methodologies.1 Introduction2 Mono-catalysis2.1 Change of Reaction Conditions2.2 Change of Catalyst3 Multi-catalysis3.1 Bifunctional Catalysis3.2 Sequential/Cascade Catalysis3.3 Synergistic/Cooperative Catalysis4 Conclusions and Outlook

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“…Recently,w ei dentified that the 7-azaindoline amides erved as al atent enolate in the carboxylic acid oxidation state in the contexto fs oft Lewis acid/hard Brønsted base cooperative catalysis. [12,13] Based on the rich chemistryo ft he azide functionality in organic synthesis, [14] we focused on the a-azidoa mide as al atent enolatet oi nstallt he azido group, whichc an be used as am asked amine and for azide-specific reactions. The use of a-azido carbonyl compounds for enolate chemistry has been scarcely explored in aldol reactions, [15] and to the best of our knowledge, no example of aM annich reaction is reported in the literature.…”

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confidence: 99%

“…As imilar trend was observed for Brsubstituted imines 3j and 3k but o-F substituted imine 3i gave the product 6i with high enantioselectivity,s uggesting that steric factors were responsible for the loss in enantioselectivity (entries8-11). Other imines, for example, p-CF 3 substituted imine 3l and heteroaromatic imines 3m and 3n,c ould be used in the present protocol to give the product with highs tereoselectivity (entries [12][13][14]. The thienyl group might competitively coordinate to the Cu I catalystt or etard the reaction and al ongerr eaction time was needed( entry 14).…”

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confidence: 99%