Chiral Monophosphorus Ligands for Asymmetric Catalytic Reactions

Fu, Wen‐Zhen; Tang, Wenjun

doi:10.1021/acscatal.6b01001

Cited by 213 publications

(99 citation statements)

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“…This specific mode of activation of multiple bonds enables a plethora of unusual transformations [1][2][3][4][5][6][7][8][9][10][11]. Considering the enantioselective transformations catalyzed by gold compounds [12][13][14][15][16][17][18][19][20][21], the main difficulty arises from the structural features of the respective complexes. Gold(I) complexes exhibit a linear geometry with unrestricted rotation around L-Au as well as Au-substrate bonds (Figure 1) [22][23][24][25].…”

Section: Introductionmentioning

confidence: 99%

Chiral N-heterocyclic Carbene Gold Complexes: Synthesis and Applications in Catalysis

Michalak

Kośnik

2019

Catalysts

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N-Heterocyclic carbenes have found many applications in modern metal catalysis, due to the formation of stable metal complexes, and organocatalysis. Among a myriad of N-heterocyclic carbene metal complexes, gold complexes have gained a lot of attention due to their unique propensity for the activation of carbon-carbon multiple bonds, allowing many useful transformations of alkynes, allenes, and alkenes, inaccessible by other metal complexes. The present review summarizes synthetic efforts towards the preparation of chiral N-heterocyclic gold(I) complexes exhibiting C 2 and C 1 symmetry, as well as their applications in enantioselective catalysis. Finally, the emerging area of rare gold(III) complexes and their preliminary usage in asymmetric catalysis is also presented. Scheme 3. The synthesis of a gold(I) complex from (R)-1-aminotetralin.An elegant approach to C2-symmetric gold(I) complexes was described by Czekelius et al. [72] (Scheme 4), inspired by previous Herrmann's work [73]. The synthetic approach involves chiral amines 24, readily available from the corresponding phenylacetic acid 22 via the Friedel-Crafts reaction of bromobenzene and fractional crystallization of the corresponding tartaric acid amine salt upon reductive amination. The resulting amine 24 was further formylated and subjected to Bischler-Napieralski cyclization to give 3-aryl-substituted dihydroisoquinoline 25. Subsequent reductive coupling afforded the basic diamine skeleton 26 into a single diastereomer, which appeared a perfect platform for structural ligand diversification via Suzuki coupling. The functionalized diamines 26 were then cyclized into imidazolium salts 27 with triethyl orthoformate to give the products with yields in the range of 49-94% (for selected examples, see Scheme 4). The formation of gold(I) complexes 28 was accomplished under rather unusual conditions, by the reaction of gold(I) chloride with a carbene generated by the action of KOtBu. Scheme 4. The synthesis of C2-symmetric gold(I) complexes accessible via a reductive coupling. The application of other chiral building blocks has recently been reported by the Toste group (Scheme 5) [74]. Besides chiral amines, amino alcohols 29 were also utilized in the synthesis of C2-Scheme 3. The synthesis of a gold(I) complex from (R)-1-aminotetralin.An elegant approach to C 2 -symmetric gold(I) complexes was described by Czekelius et al. [72] (Scheme 4), inspired by previous Herrmann's work [73]. The synthetic approach involves chiral amines 24, readily available from the corresponding phenylacetic acid 22 via the Friedel-Crafts reaction of bromobenzene and fractional crystallization of the corresponding tartaric acid amine salt upon reductive amination. The resulting amine 24 was further formylated and subjected to Bischler-Napieralski cyclization to give 3-aryl-substituted dihydroisoquinoline 25. Subsequent reductive coupling afforded the basic diamine skeleton 26 into a single diastereomer, which appeared a perfect platform for structural ligand diversification via Suzuki...

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Section: Introductionmentioning

confidence: 99%

Chiral N-heterocyclic Carbene Gold Complexes: Synthesis and Applications in Catalysis

Michalak

Kośnik

2019

Catalysts

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“…These resultss et the stage for facile access to as eries of new chiral monodentate phosphoramidites 6a-m,s tarting from the enantiopure 2,2'-dimethyl-substituted, cyclopentyl-fused, or cyclohexyl-fused spirobiindane-diols 5a-f.O wing to their modular structure and facile synthesis, av ariety of mono-phosphora- Entry Spirobiindane-diolDihedral angle [8] [b] O1···O2 distance [] [c] 1 [a] 86.247 (122) www.chemeurj.org midites have been established as highly versatile chirall igands in transition metal catalysis, with widespread applicationsi n numerous asymmetric transformations. [15] Since it is well known that the aminog roup can substantially influencet he catalytic performance of the resulting phosphoramidite ligand, severalt ypes of amines with distinct stereoelectronic features were used in combination with spirobiindane-diols 5a-f to build phosphoramidite ligands for fine-tuning catalysis. As shown in Scheme2,t reatment of enantiopure diols 5a-f with an aminophosphorus dichloride( Cl 2 PNR 2 )i nt he presence of triethylamine led to ready formation of corresponding chiral spiro mono-phosphoramidite ligands 6a-m,r espectively,i na single step.…”

Section: Synthesis Of Chiral Monodentate Phosphoramidite Ligandsmentioning

confidence: 99%

Development of Chiral Spiro Phosphoramidites for Rhodium‐Catalyzed Enantioselective Reactions

Zheng

Cao

Zhu

et al. 2019

Chemistry A European J

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Aseries of 1,1'-spirobiindane-7,7'-diol (SPINOL)a nalogues bearing a2 ,2'-dimethyl-, cyclopentyl-, or cyclohexylfused ring weres ynthesized, and their distinct structural features were elucidated by X-ray crystallography. On the basis of these scaffolds,c hiral monophosphoramidite ligands 6am were synthesized,w hich demonstrated excellent enantioselectivity in Rh I -catalyzed asymmetric hydrogenation of a dehydro amino acid methyl ester.L igands 6a-m were also successfully applied in the Rh I -catalyzed enantioselective [4+ +2] cycloaddition of a,b-unsaturated imines with isocyanates,w hicha fforded the corresponding pyrimidinones in good yields (60-92 %) with high enantioselectivities (75-92 % ee).Scheme1.a) Synthesisofc hiral 2,2'-dimethylspirobiindanediols. b) Synthesis of chiral cyclopentyl-or cyclohexyl-fusedspirobiindanediols. Conditions: i) NaH (3.0 equiv),T HF,08C, 1h,t hen MeI (3.0 equiv), 0 8C!RT;ii) PPA, 105 8C, 6h;iii) nBuLi (3.0 equiv), THF, À78 8C, 1h;i v) BBr 3 (2.5 equiv), CH 2 Cl 2 , À78 8C!RT,12h; v) optical resolution by semipreparative HPLC on ac hiralcolumn.

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“…The central point of these studies is the chirality transfer in the variety of forms. XXII Among them, we can mention the stereo-physics of liquid crystals [126] and chiral catalysis [169]. The modeling macroscopic chirality emerged from the chiral molecular elements is a challenge for theory, computations, and experiments [126].…”

Section: Chirality Transfermentioning

confidence: 99%

The Chain of Chirality Transfer as Determinant of Brain Functional Laterality. Breaking the Chirality Silence: Search for New Generation of Biomarkers; Relevance to Neurodegenerative Diseases, Cognitive Psychology, and Nutrition Science

Dyakin¹,

Lucas²,

Dyakina‐Fagnano³

et al. 2017

NNR

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Chiral Monophosphorus Ligands for Asymmetric Catalytic Reactions

Cited by 213 publications

References 345 publications

Chiral N-heterocyclic Carbene Gold Complexes: Synthesis and Applications in Catalysis

Chiral N-heterocyclic Carbene Gold Complexes: Synthesis and Applications in Catalysis

Development of Chiral Spiro Phosphoramidites for Rhodium‐Catalyzed Enantioselective Reactions

The Chain of Chirality Transfer as Determinant of Brain Functional Laterality. Breaking the Chirality Silence: Search for New Generation of Biomarkers; Relevance to Neurodegenerative Diseases, Cognitive Psychology, and Nutrition Science

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