F<sub>8</sub>BINOL, an Electronically Perturbed Version of BINOL with Remarkable Configurational Stability

Yudin, Andrei K.; Martyn, L. James P.; Pandiaraju, Subramanian; Zheng, and Juan; Lough, Alan J.

doi:10.1021/ol991244v

Cited by 68 publications

(46 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The Ullmann coupling similar to what had been tried in the synthesis of 3 gave 9 in only 5% yield [8]. The major product was the protected F 8 BINOL derivative, obtained in 85% yield (Scheme 2).…”

Section: Resultsmentioning

confidence: 82%

“…The derivative 19 reacted with phosphorous oxychloride to generate the corresponding sulfonyl chloride 20 (Scheme 7). Coupling of alcohol 21, prepared by demethylation of 4 with boron tribromide [8], with 20 in the presence of triethylamine gave the desired intermediate for the radical cross-coupling reaction (Scheme 8). The cross-coupling was carried out in the presence of 1-ethylpiperidine hypophosphite (EPHP) and AIBN in benzene at 70 8C for 2 days and gave the product in 65% conversion and 58% yield [24,25].…”

Section: Other Cross-coupling Methodsmentioning

confidence: 99%

“…Column chromatographic purifications were performed using silica gel with 230-400 mesh size. Compounds 4 and 16 were prepared according to literature procedures [8]. Characterization for compound 20 was verified according to literature [27].…”

Section: General Considerationsmentioning

confidence: 99%

“…13 C NMR (100 MHz, CDCl 3 ) d 156. 8,154.7,137.0,136.7,133.5,132.6,129.6,128.8,128.6,128.5,128.4,128.35,128.3,128.25,128.24,128.20,128.0,127.8,127.7,127.6,127.5,126.8,125.8,121.2,119.1,119.0,116.4,107.2,71.5,70.1,6,1 0 ]-binaphthalenyl-2,2 0 -diol (26) To a solution of 2 (50 mg, 0.14 mmol) in dry Et 2 O (2 ml) was added t-BuLi (1.7 M in pentane, 0.42 mmol) at À78 8C. The reaction was stirred at À78 8C for 2 h, then warmed to room temperature and stirred overnight.…”

Section: 2 0 -Bismentioning

confidence: 99%

“…This interest was driven by the known stability of the C-F bond towards oxidation [5], propensity of fluoroaromatics to engage in stabilizing stacking interactions with other aromatic rings [6], and rich nucleophilic aromatic substitution chemistry of fluoroaromatic compounds [7]. We recently, published the synthesis and catalytic applications of polyfluorinated BINOL ligands such as F 8 BINOL (3), an electronic isostere of BINOL [8]. In terms of catalytic applications, we explored the sulfoxidation [9] as well as the glyoxylateene reaction [10].…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Preparation and catalytic applications of partially fluorinated binaphthol ligands

Yekta

Krasnova

Mariampillai

et al. 2004

Journal of Fluorine Chemistry

Self Cite

View full text Add to dashboard Cite

Section: Resultsmentioning

confidence: 82%

Section: Other Cross-coupling Methodsmentioning

confidence: 99%

Section: General Considerationsmentioning

confidence: 99%

Section: 2 0 -Bismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Preparation and catalytic applications of partially fluorinated binaphthol ligands

Yekta

Krasnova

Mariampillai

et al. 2004

Journal of Fluorine Chemistry

Self Cite

View full text Add to dashboard Cite

An Effective and Useful Synthesis of Enantiomerically Enriched Arylglycinols

Bandini

Cozzi

Gazzano³

et al. 2001

Eur. J. Org. Chem.

View full text Add to dashboard Cite

A two-step synthesis of racemic arylglycinols, together with a simple and straightforward methodology for their resolution, is described. This method constitutes a practical means of preparing racemic and optically pure electron-rich or electron-poor substituted arylglycinols, useful building blocks for the synthesis of biologically active molecules and chiral ligands. All of the chiral β-amino alcohols 5−8 were isolated in good chemical yields and with excellent enantiomeric ex-

show abstract

IAN-Amines: Direct Entry to a ChiralC2-Symmetric Zirconium(IV)β-Diketimine Complex

Cortright

Johnston

2002

Angew. Chem.

View full text Add to dashboard Cite

The immense utility of metallocene-based catalysts for synthesis [1] has stimulated the development of non-metallocene complexes that conserve metallocene topographies but offer a greater degree of accessibility and/or improved performance. [2] A number of recent publications have demonstrated that amidinate ligands, [3,4] b-diketimines, [5±7] and other variations on the [1,n]-bisimine template are promising in this regard for group IV metals. In general, ligands used as the basis for a non-metallocene complex must 1) bind to the stereochemistry of 5 d was deduced clearly by means of X-ray crystallography. This tandem cyclization was also applied to allene ketones. Thus allene ketone 4 e was cyclized to give piperidyl-substituted alcohol 5 e in 67 % yield (Table 2, entry 5). However, the malonate substrate 4 f gave rise to cis-cyclohexanol 5 f (30 %) as well as the simple addition product 6 (35 %) ( Table 2, entry 6).The exact mechanism of this cis-stereoselective tandem reaction has yet to be elucidated. It is presumed that Me 3 SiPdSnBu 3 adds initially to the allene moiety to give sor p-allyl palladium complexes, which undergo intramolecular carbonyl allyl addition to afford cis-cycloalkanols. The cis selectivity of the reaction can be ascribed to the fact that intermediate A, which leads to the cis-cyclopentanol, is energetically more stable than B, presumably because of the steric hindrance between TMS and R (R H, Me) groups (Scheme 2). [11] In summary, the palladium-catalyzed regio-and diastereoselective tandem silastannylation/carbonyl allyl addition of allene aldehydes and ketones gives rise to cis-cycloalkanols. The process requires a single catalyst and is carried out at constant temperature. Experimetal SectionTypical procedure: trimethyl(tributylstannyl)silane 2 (150 mg, 0.41 mmol) was added to a stirred solution of 1 a (100 mg, 0.38 mmol) and (pallyl) 2 Pd 2 Cl 2 (6.9 mg, 5 mol %) in THF (3 mL). The reaction mixture was stirred room temperature for 10 min, and the THF solvent was evaporated in vacuo. The crude product was separated by means of column chromatography (EtOAc/hexane 1:2) to afford the cyclized product 3 a (91 mg, 71 %) as a white solid. M.p. 95 8C; R f 0.41 (EtOAc/hexane 1:2); The condensation of allylic stannanes and aldehydes catalyzed by the known palladium and platinum complexes was primarily limited to simple allylic stannanes and crotyl stannanes; see: H.

show abstract

F₈BINOL, an Electronically Perturbed Version of BINOL with Remarkable Configurational Stability

Cited by 68 publications

References 15 publications

Preparation and catalytic applications of partially fluorinated binaphthol ligands

Preparation and catalytic applications of partially fluorinated binaphthol ligands

An Effective and Useful Synthesis of Enantiomerically Enriched Arylglycinols

IAN-Amines: Direct Entry to a ChiralC2-Symmetric Zirconium(IV)β-Diketimine Complex

Contact Info

Product

Resources

About

F8BINOL, an Electronically Perturbed Version of BINOL with Remarkable Configurational Stability

Cited by 68 publications

References 15 publications

Preparation and catalytic applications of partially fluorinated binaphthol ligands

Preparation and catalytic applications of partially fluorinated binaphthol ligands

An Effective and Useful Synthesis of Enantiomerically Enriched Arylglycinols

IAN-Amines: Direct Entry to a ChiralC2-Symmetric Zirconium(IV)β-Diketimine Complex

Contact Info

Product

Resources

About

F₈BINOL, an Electronically Perturbed Version of BINOL with Remarkable Configurational Stability