Ligand-Controlled Stereodivergent, Enantioselective Conjugate Addition of 2-Oxazoline- and 2-Thiazoline-4-carboxylate to Nitroalkene Catalyzed by Chiral Copper Complexes

Matsuda, Yukiko; Koizumi, Akihiro; Haraguchi, Ryosuke; Fukuzawa, Shin‐ichi

doi:10.1021/acs.joc.6b01722

Cited by 20 publications

(10 citation statements)

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“…The Fukuzawa's group further extended their diastereodivergent approach towards the Michael addition of 2‐oxazoline‐ and 2‐thiazoline‐4‐carboxylates 197 (analogues of 192 ) to nitroalkenes 24 (Scheme ) . The diastereodivergence was obtained by choosing appropriate chiral ligands with the copper(I) catalyst.…”

Section: Metal Complex‐catalyzed Diastereodivergent Reactionsmentioning

confidence: 99%

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: 99%

Advances in Asymmetric Diastereodivergent Catalysis

2017

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“…Nitromethane conjugate addition products are commonly used to prepare biologically relevant heterocycles such as spiro‐γ‐lactams, pyrrolidines, and diarylpyrrolines and their isostere N ‐oxides . Thus, the reduction of the nitro groups of β‐(nitromethyl)chromones 2a – 2d was considered for the preparation of primary amine derivatives.…”

Section: Resultsmentioning

confidence: 99%

1,6‐Conjugate Additions of Carbon Nucleophiles to 2‐[(1E,3E)‐4‐Arylbuta‐1,3‐dien‐1‐yl]‐4H‐chromen‐4‐ones

et al. 2017

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The 1,6‐conjugate addition of nitromethane to 2‐[(1E,3E)‐4‐arylbuta‐1,3‐dien‐1‐yl]‐4H‐chromen‐4‐ones was accomplished and led mainly to the corresponding β‐(nitromethyl)chromones. (E)‐5′‐(Nitromethyl)‐3′‐styryl‐[1,1′‐biphenyl]‐2‐ol and 3′‐aryl‐2′‐nitro‐5′‐(nitromethyl)spiro[chromane‐2,1′‐cyclohexan]‐4‐one derivatives were also isolated as minor products from tandem processes, which result from the addition of a second molecule of nitromethane. The nucleophile scope was investigated with malononitrile, acetylacetone, ethyl cyanoacetate, and diethyl malonate, which gave the expected 1,6‐addition products; in the last case, it was also possible to isolate a minor product formed through a 1,8‐/1,6‐addition sequence. Computational calculations provided a rationale for the experimental reactivity of carbon nucleophiles with 2‐[(1E,3E)‐4‐arylbuta‐1,3‐dien‐1‐yl]‐4H‐chromen‐4‐ones. The further functionalization of some adducts allowed the preparation of new nitrogen‐containing heterocyclic compounds, such as new styrylpyrrolidines and new pyrazole and bis(pyrazole) derivatives.

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“…Hou reported that tuning the electric properties of the phosphorus atoms on FOXAP ligands leads to chiral pyrrolidines via 1,3‐dipolar cycloaddition in exo and endo conformations, and each diastereomer was obtained with high selectivity . Asymmetric stereodivergent synthesis promoted by ferrocene‐type ligands was also developed by Cossío, Wang, and Fukuzawa . Because of these encouraging advances, the exploration of diastereomer‐specific ferrocenyl ligands is emerging.…”

Section: Discussionmentioning

confidence: 99%

Chiral Oxazolinyl Hydroxyl Ferrocene Catalysts: Synthesis and Applications in Asymmetric Reactions

Zhang

Dai

2020

ChemistrySelect

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Chiral oxazolinyl hydroxyl ferrocenes have been demonstrated as representative catalysts in enantioselective nucleophilic addition reactions in the last few decades. They have received much interest from chemists because of not only the numerous substitution patterns at their sandwich backbones, but also their superior catalytic activity in asymmetric transformations. Recent research has revealed that the planar chirality of these catalysts influences the stereochemistry of asymmetric products and the application scope in enantioselective reactions. Herein, we provide an intensive survey of chiral oxazolinyl hydroxyl ferrocene compounds, including the structures of chiral compounds already published, designed synthetic approaches for ferrocenes with different patterns, and their utilization in the enantioselective preparation of secondary alcohols using organozinc reagents.

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Ligand-Controlled Stereodivergent, Enantioselective Conjugate Addition of 2-Oxazoline- and 2-Thiazoline-4-carboxylate to Nitroalkene Catalyzed by Chiral Copper Complexes

Cited by 20 publications

References 15 publications

Advances in Asymmetric Diastereodivergent Catalysis

Advances in Asymmetric Diastereodivergent Catalysis

1,6‐Conjugate Additions of Carbon Nucleophiles to 2‐[(1E,3E)‐4‐Arylbuta‐1,3‐dien‐1‐yl]‐4H‐chromen‐4‐ones

Chiral Oxazolinyl Hydroxyl Ferrocene Catalysts: Synthesis and Applications in Asymmetric Reactions

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