Chiral 1,1′‐Binaphthyl‐2,2′‐Disulfonic Acid (BINSA) and Its Derivatives for Asymmetric Catalysis

Hatano, Manabu; Ishihara, Kazuaki

doi:10.1002/ajoc.201300256

Cited by 35 publications

(15 citation statements)

References 74 publications

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“…-H bond functionalization because the BINSate can easily dissociate from the metal center to provide vacant coordination sites due to its high acidity 45. Treatment of (S)-BINSA 1a with Ag 2 CO 3 followed by [Cp*RhCl 2 ] 2 in CH3 CN afforded [Cp*RhL N ][(S)-BINSate] 2a (Fig.…”

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confidence: 99%

Pentamethylcyclopentadienyl rhodium(III)–chiral disulfonate hybrid catalysis for enantioselective C–H bond functionalization

et al. 2018

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Although Cp*Rh(III) complexes are prominent and versatile catalysts for C-H bond functionalization reactions, catalytic stereocontrol is difficult due to the lack of vacant coordination sites. Here we report a hybrid strategy for inducing chirality without using previously reported chiral Cp x ligands. A preformed hybrid catalyst, [Cp*RhL N ][6,6'-Br-(S)-BINSate], catalyzed C-H activation and subsequent conjugate addition of 2-phenylpyridine derivatives to enones in good yield and enantioselectivity (up to 95:5 er). In addition to 2-phenylpyridines, conjugate addition of 6-arylpurines proceeded in up to 91:9 er using [Cp*RhL N ][(R)-SPISate]. The results demonstrated that a chiral organic anion can efficiently control the enantioselectivity of Cp*Rh(III)-catalyzed C-H bond functionalization without a chiral Cp x ligand. Transition metal catalysts cleave inert carbon-hydrogen (C-H) bonds in organic molecules to form reactive organometallic intermediates, enabling catalytic transformation of C-H bonds to desired carbon-carbon and carbon-heteroatom bonds. This catalytic C-H bond functionalization strategy can facilitate the development of atom-1 and step-economical 2 syntheses of functional molecules, and thus has been intensively investigated over the several decades. 3-16 Among various types of transition metal catalysts studied for catalytic C-H bond functionalization, Rh(III) complexes bearing a pentamethylcyclopentadienyl (Cp*) or related cyclopentadienyl-type (Cp,

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Pentamethylcyclopentadienyl rhodium(III)–chiral disulfonate hybrid catalysis for enantioselective C–H bond functionalization

et al. 2018

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“…Although the sulfonamide catalyst 16 was inefficient, [22] the reaction catalyzed by Tf 2 NH afforded 12a in 24% yield (entries 9–10). As shown in entries 11–12, the aza-Friedel–Crafts cyclization was achieved more efficiently at room temperature upon catalysis with BINSA-K 17 [23] and TfOH to obtain the lactone scaffold 12a in 38% and 56% yields respectively. Interestingly, most of the sulfonimide- and sulfonate-derived catalysts tested in the reaction provided product 12a (entries 7–12), in comparison to other Brønsted acid catalysts with lower pKas, suggesting a possible counteranion effect on the aza-Friedel–Crafts reactivity, potentially due to a stabilization of iminium 11a .…”

Section: Resultsmentioning

confidence: 99%

Total synthesis of (±)-fumimycin and analogues for biological evaluation as peptide deformylase inhibitors

et al. 2019

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A concise 7-step total synthesis of (±)-fumimycin in 11.6 % overall yield is reported. An acidcatalyzed intramolecular aza-Friedel-Crafts cyclization was developed to construct the benzofuranone skeleton of the natural product bearing an α,α-disubstituted amino acid moiety in a single step. Regioselective chlorination followed by a Suzuki-Miyaura cross-coupling rapidly enabled the preparation of a library of analogues which were evaluated against peptide deformylase for antibacterial activity.

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“…We focused our attention on 1,1'-binaphthyl-2,2'-disulfonic acid (BINSA) and its dianion (BINSate) as an external source of chirality, 61,62 speculating that the high acidity of sulfonic acid and the low coordinating ability of the sulfonate anion could lead to high reactivity of cationic Cp*M III catalysts, where the coordination of anions usually inhibit the productive reaction pathways.…”

Section: Cp*rh III /Chiral Disulfonate Catalysts For Enantioselectivementioning

confidence: 99%

Cp*CoIII-Catalyzed C–H Functionalization and Asymmetric Reactions Using External Chiral Sources

Yoshino¹,

Matsunaga²

2019

Synlett

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This account describes Cp*CoIII-catalyzed C–H functionalization reactions developed in our group between 2013 and 2018. Cp*CoIII catalysts not only serve as inexpensive alternatives to Cp*RhIII catalysts but also exhibit unique reactivity and selectivity in several transformations. In the latter part of this review, we introduce catalytic asymmetric C–H functionalization reactions using achiral RhIII or CoIII catalysts with chiral disulfonates or carboxylic acids as external chiral sources.1 Introduction and Overview2 Cp*CoIII-Catalyzed C–H Functionalization Reactions2.1 C–H Addition Reactions to Polar Double Bonds2.2 Cp*Co(CO)I2 and [Cp*CoI2]2 Precursors for the C2-selective C–H Amidation of Indoles2.3 C–H Functionalization of Carbamoyl-Protected Indoles Using Alkynes2.4 C–H Allylation Using Allyl Alcohols2.5 Cyclization Reactions of O-Acyloximes and Alkynes2.6 Other Miscellaneous Reactions3 Enantioselective C–H Functionalization Reactions by Hybrid Catalysis3.1 Cp*RhIII/Chiral Disulfonate Catalysts for the Enantioselective C–H Addition to Enones3.2 Enantioselective C–H Cleavage Using Chiral Carboxylic Acids4 Summary and Perspective

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Chiral 1,1′‐Binaphthyl‐2,2′‐Disulfonic Acid (BINSA) and Its Derivatives for Asymmetric Catalysis

Cited by 35 publications

References 74 publications

Pentamethylcyclopentadienyl rhodium(III)–chiral disulfonate hybrid catalysis for enantioselective C–H bond functionalization

Pentamethylcyclopentadienyl rhodium(III)–chiral disulfonate hybrid catalysis for enantioselective C–H bond functionalization

Total synthesis of (±)-fumimycin and analogues for biological evaluation as peptide deformylase inhibitors

Cp*CoIII-Catalyzed C–H Functionalization and Asymmetric Reactions Using External Chiral Sources

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