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Volumn 9, Issue 20, 2007, Pages 3969-3972

Stereochemical control of both C-C and C-N axial chirality in the synthesis of chiral N-O biaryls

Author keywords

[No Author keywords available]

Indexed keywords

CARBON; NITROGEN;

EID: 35048839171     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol701692m     Document Type: Article
Times cited : (91)

References (74)
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    • 1455. For a comprehensive review on the synthesis of ynamides, see
    • (c) Katritzky, A. R.; Jiang, R.; Singh, S. K. Heterocycles 2004, 63, 1455. For a comprehensive review on the synthesis of ynamides, see:
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    • Terrahedron-Symposium-In-Print: Chemistry of Electron-Deficient Ynamines and Ynamides
    • For a special issue dedicated to the chemistry of ynamides, see:, Issue No
    • For a special issue dedicated to the chemistry of ynamides, see: Terrahedron-Symposium-In-Print: Chemistry of Electron-Deficient Ynamines and Ynamides. Tetrahedron 2006, 62, Issue No. 16.
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    • For recent reviews, see: a
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    • For a review, see
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    • For some elegant examples of axially chiral amido-aryl bonds: a
    • For some elegant examples of axially chiral amido-aryl bonds: (a) Kitagawa, O.; Takahashi, M.; Yoshikawa, M.; Taguchi, T. J. Am. Chem. Soc. 2005, 127, 3676.
    • (2005) J. Am. Chem. Soc , vol.127 , pp. 3676
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    • 2. They led to lower yields and/or ee's.
    • 2. They led to lower yields and/or ee's.
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    • See the Supporting Information. General procedure: To a solution of [Rh(cod)2]BF4 (10 mol , and (S)-xylyl-BINAP (10 mol , in anhyd 1,2-dichloroethane (5.0 mM) was added 4 Å molecular sieves in a sealed tube. The mixture was stirred at rt for 10 min before a respective ynamide (1.00 mmol) and diyne (2.00 mmol) were added. The solution was heated to 85 °C and followed by LCMS. After the reaction was complete, the solution was cooled to rt and filtered through a short pad of silica gel. Elution with EtOAc/hexanes (1:1) followed by concentration in vacuo afforded a crude mixture of diastereomers. Separation and purification of the resulting crude residue via silica gel flash column chromatography (gradient eluent: EtOAc in hexanes) afforded the desired N, O-biaryl diastereomers. Diastereomeric ratios were found in the crude 1H NMR, and the enantiomeric excess of each diastereomer was determined via chiral HPLC [CHIRALCEL OD-H; 250 × 4.6 mm
    • 1H NMR, and the enantiomeric excess of each diastereomer was determined via chiral HPLC [CHIRALCEL OD-H; 250 × 4.6 mm (I × i.d.); eluent: i-PrOH in hexanes].
  • 68
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    • Throughout the paper, the capital M and P denote C-C axial chirality while small m and p denote C-N axial chirality and are listed second.
    • Throughout the paper, the capital M and P denote C-C axial chirality while small m and p denote C-N axial chirality and are listed second.
  • 69
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    • Upon a clean and facile separation on silica gel flash column chromatography, and after removal of the solvent under reduced pressure without heating, the two atropisomers of 19 have already scrambled based on NMR analysis. This prevented us from obtaining any meaningful ratios.
    • Upon a clean and facile separation on silica gel flash column chromatography, and after removal of the solvent under reduced pressure without heating, the two atropisomers of 19 have already scrambled based on NMR analysis. This prevented us from obtaining any meaningful ratios.
  • 70
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    • For elegant examples of achiral template based asymmetric catalysis, see: a
    • For elegant examples of achiral template based asymmetric catalysis, see: (a) Sibi, M. P.; Soeta, T. J. Am. Chem. Soc. 2007, 129, 4522.
    • (2007) J. Am. Chem. Soc , vol.129 , pp. 4522
    • Sibi, M.P.1    Soeta, T.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.