BINOL-derived bifunctional sulfide catalysts for asymmetric synthesis of 3,3-disubstituted phthalides <i>via</i> bromolactonization

Okada, Megumi; Kaneko, Kazuma; Yamanaka, Masahiro; Shirakawa, Seiji

doi:10.1039/c9ob00417c

Cited by 46 publications

(20 citation statements)

References 48 publications

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“…The highest performance for 2 aa was almost maintained even when the reaction was carried out with only 2 mol % of Zn(OH) 2 and L17 (96% ee). On the basis of these reaction profiles, we estimated that our reaction system should be advantageous for the preparation of highly enantioenriched 3,3-disubstituted phthalides [32] possessing a synthetically useful carbonyl functionality on its side chain. Thus, use of methyl 2acetylbenzoate as a substrate was found to give 3 in one pot via spontaneous cyclization of the resulting adduct (93% yield, 94% ee).…”

Section: Full Papermentioning

confidence: 99%

Zinc Hydroxide‐Catalyzed Asymmetric Allylation of Acetophenones with Amido‐Functionalized Allylboronate in Water

et al. 2020

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Enantioselective allylation of aldehydes and ketones is a widely used approach for preparing chiral homoallylic alcohols, however, most of the reactions are still mainly performed in organic solvents. Considering their environmental impact, expansion of synthetic technology in water has the highest priority in the organic chemistry field. Here, we report enantioselective reaction of water‐stable amido‐functionalized allylboronates with acetophenone derivatives in water. The reaction was catalyzed with zinc hydroxide and a didecylamino‐functionalized chiral aminophenol reagent, affording a variety of homoallylic alcohols in up to 99% yield. There is a definite proportional correlation between the enantioselectivity and the size of an ortho‐substituent on the substrate, and the enantiomeric excess of the product reached up to 98%.

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Section: Full Papermentioning

confidence: 99%

Zinc Hydroxide‐Catalyzed Asymmetric Allylation of Acetophenones with Amido‐Functionalized Allylboronate in Water

et al. 2020

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“…Simultaneously, a carboxylic acid moiety on substrate 1 a is activated by the succinimide anion that served as a Brønsted base to provide a wellorganized transition state (TS), as in B. A plausible 3D structure of the TS model, which was proposed based on the DFT calculations of our previous reports, [4] is also shown in Scheme 3. Stereoselective intramolecular cyclization then proceeds to yield an optically active γ-butyrolactone product 2 a with the regeneration of catalyst (S)-3.…”

Section: Resultsmentioning

confidence: 91%

Chiral Bifunctional Sulfide‐Catalyzed Highly Enantioselective Bromolactonizations of 4‐Pentenoic Acids

et al. 2021

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Despite extensive studies into the design of effective chiral catalysts for asymmetric halolactonizations, the development of highly enantioselective catalytic bromolactonization of 4-aryl-4-pentenoic acids, which is one of the benchmark reactions, has not been completely satisfactory. Herein, we report the use of BINOL-derived chiral bifunctional sulfide catalysts to achieve highly enantioselective bromolactonizations of 4-aryl-4-pentenoic acids. The importance of the bifunctional design of chiral sulfide catalysts was clearly demonstrated in the present study. Furthermore, the present catalytic asymmetric reaction system could be applied to highly stereoselective desymmetrizing bromolactonizations.

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“…The requisite chiral bifunctional selenide catalysts ( S )‐ 1 can be readily prepared from the known compounds ( S )‐ 6 (Scheme ) . The arylmethyl bromide moiety of compounds ( S )‐ 6 was treated with a commercially available phenylselenol in the presence of potassium carbonate to provide selenides ( S )‐ 7 .…”

Section: Methodsmentioning

confidence: 99%

Chiral Bifunctional Selenide Catalysts for Asymmetric Bromolactonization

2020

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The development of chiral selenium catalysts for asymmetric transformations has become a pre‐eminent topic in the field of organocatalytic chemistry. Herein, we report the development of chiral bifunctional selenide catalysts bearing a hydroxy group and discuss their application to asymmetric bromolactonization reactions. The importance of the bifunctional design of chiral selenide catalysts for enantioselective bromolactonizations was clearly demonstrated in the present work.

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BINOL-derived bifunctional sulfide catalysts for asymmetric synthesis of 3,3-disubstituted phthalides via bromolactonization

Abstract: An efficient enantioselective synthesis of 3,3-disubstituted phthalides possessing a chiral quaternary carbon center was achieved via catalytic asymmetric bromolactonization using BINOL-derived bifunctional sulfide catalysts.

Cited by 46 publications

References 48 publications

Zinc Hydroxide‐Catalyzed Asymmetric Allylation of Acetophenones with Amido‐Functionalized Allylboronate in Water

Zinc Hydroxide‐Catalyzed Asymmetric Allylation of Acetophenones with Amido‐Functionalized Allylboronate in Water

Chiral Bifunctional Sulfide‐Catalyzed Highly Enantioselective Bromolactonizations of 4‐Pentenoic Acids

Chiral Bifunctional Selenide Catalysts for Asymmetric Bromolactonization

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