(aS)-7'-bromo-2,2'-dimethoxy-3-(methoxymethyl)-1,1'-binaphthalene | 249744-32-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (aS)-7'-bromo-2,2'-dimethoxy-3-(methoxymethyl)-1,1'-binaphthalene
• 英文别名: (+/-)-7'-bromo-2,2'-dimethoxy-3-(methoxymethyl)-1,1'-binaphthalene；1-(7-Bromo-2-methoxynaphthalen-1-yl)-2-methoxy-3-(methoxymethyl)naphthalene；1-(7-bromo-2-methoxynaphthalen-1-yl)-2-methoxy-3-(methoxymethyl)naphthalene
• CAS: 249744-32-9
• 化学式: C₂₄H₂₁BrO₃
• 分子量: 437.333
• InChiKey: OWXFGUGNBIHJRZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (aS)-7'-bromo-2,2'-dimethoxy-3-(methoxymethyl)-1,1'-binaphthalene 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 76.17h， 生成 (aS,2S,4S,5R)-1-[4-(trifluoromethyl)benzyl]-2-[(R)-(2,2'-dimethoxy-3'-(methoxymethyl)-1,1'-binaphthalen-7-yl)hydroxymethyl]-5-ethylazoniabicyclo[2.2.2]octane bromide
  参考文献：
  名称：

  Asymmetric Phase-Transfer Catalysis by Quaternary Ammonium Ions Derived fromCinchona-Alkaloid Analogs Containing 1,1′-Binaphthalene Moieties

  摘要：

  The synthesis and catalytic properties of a new type of enantioselective phase-transfer catalysts, incorporating both the quinuclidinemethanol fragment of Cinchona alkaloids and a 1,1'-binaphthalene moiety, are described. Catalyst (+)-(aS,3R,4S,8R,9S)-4 with the quinuclidine fragment attached to C(7') in the major groove of the 1,1'-binaphthalene residue was predicted by computer modeling to be an efficient enantioselective catalyst for the unsymmetric alkylation of 6,7-dichloro-5-methoxy-2-phenylindanone (1; Scheme I, Fig. I). Its synthesis involved the selective oxidative cross-coupling of two differently substituted naphthalen-2-ols to afford the asymmetrically substituted 1,1'-binaphthalene derivative (+/-)-17 in high yield (Scheme 3). Chromatographic optical resolution via formation of diastereoisomeric camphorsulfonyl esters and functional-group manipulation gave access to the 7-bromo-1,1'-binaphthalene derivative (-)-(aS)-11 (Scheme 4). Nucleophilic addition of lithiated (-)-(aS)-11 to the quinuclidine Weinreb amide (+)-(3R,4S,8R)-8 afforded the two ketones (aS,3R,4S,8R)-27 and (aS,3R,4S,8S)-28 as an inseparable mixture of diastereoisomers (Scheme 6). Stereoselective reduction of this mixture with DIBAL-H (diisobutylaluminum hydride; preferred formation of the C(8)-C(9) erythro-pair of diastereoisomers with 18% de) or with NaBH4 (preferred formation of the threo-pair of diastereoisomers with 50% de) afforded the four separable diastereoisomers (+)-(aS,3R,4S,8S,9S)-29, (+)-(aS,3R,4S,8R,9R)-30, (-)-(aS,3R,4S,8S,9R)-31, and (+)-(aS,3R,4S,8R,9S)-32 (Scheme 6). A detailed conformational analysis, combining H-1-NMR spectroscopy and molecular-mechanics computations, revealed that the four diastereoisomers displayed distinctly different conformational preferences (Figs. 2 and 3). These novel Cinchona-alkaloid analogs were quaternized to give (+)-(aS,3R,4S,8R,9S)-4, (+)-(aS,3R,4S,8S,9S)-5, (+)(aS,3R,4S,8R,9R)-6, and (-)-(aS,3R,4S,8S,9R)-7 (Scheme 7) which were tested as phase-transfer agents in the asymmetric allylation of phenylindanone 1. Without any optimization work, (+)-(aS,3R,4S,8R,9S)-4 was found to catalyze the allylation of 1 yielding the predicted enantiomer (+)-(S)-3b in 32% ee. The three diastereoisomeric catalysts (+)-5, (+)-6, and (-)-7 gave access to lower enantioselectivities (6 to 22% ee's), which could be rationalized by computer modeling (Fig. 4).

  DOI：

  10.1002/(sici)1522-2675(19990707)82:7<981::aid-hlca981>3.0.co;2-v
• 作为产物：
  描述：

  (aS)-methyl 7'-bromo-2,2'-dimethoxy-1,1'-binaphthalene-3-carboxylate 在 sodium hydride 、 二异丁基氢化铝 作用下， 以 正己烷 、 二氯甲烷 、 丙酮 为溶剂， 反应 3.5h， 生成 (aS)-7'-bromo-2,2'-dimethoxy-3-(methoxymethyl)-1,1'-binaphthalene
  参考文献：
  名称：

  Asymmetric Phase-Transfer Catalysis by Quaternary Ammonium Ions Derived fromCinchona-Alkaloid Analogs Containing 1,1′-Binaphthalene Moieties

  摘要：

  The synthesis and catalytic properties of a new type of enantioselective phase-transfer catalysts, incorporating both the quinuclidinemethanol fragment of Cinchona alkaloids and a 1,1'-binaphthalene moiety, are described. Catalyst (+)-(aS,3R,4S,8R,9S)-4 with the quinuclidine fragment attached to C(7') in the major groove of the 1,1'-binaphthalene residue was predicted by computer modeling to be an efficient enantioselective catalyst for the unsymmetric alkylation of 6,7-dichloro-5-methoxy-2-phenylindanone (1; Scheme I, Fig. I). Its synthesis involved the selective oxidative cross-coupling of two differently substituted naphthalen-2-ols to afford the asymmetrically substituted 1,1'-binaphthalene derivative (+/-)-17 in high yield (Scheme 3). Chromatographic optical resolution via formation of diastereoisomeric camphorsulfonyl esters and functional-group manipulation gave access to the 7-bromo-1,1'-binaphthalene derivative (-)-(aS)-11 (Scheme 4). Nucleophilic addition of lithiated (-)-(aS)-11 to the quinuclidine Weinreb amide (+)-(3R,4S,8R)-8 afforded the two ketones (aS,3R,4S,8R)-27 and (aS,3R,4S,8S)-28 as an inseparable mixture of diastereoisomers (Scheme 6). Stereoselective reduction of this mixture with DIBAL-H (diisobutylaluminum hydride; preferred formation of the C(8)-C(9) erythro-pair of diastereoisomers with 18% de) or with NaBH4 (preferred formation of the threo-pair of diastereoisomers with 50% de) afforded the four separable diastereoisomers (+)-(aS,3R,4S,8S,9S)-29, (+)-(aS,3R,4S,8R,9R)-30, (-)-(aS,3R,4S,8S,9R)-31, and (+)-(aS,3R,4S,8R,9S)-32 (Scheme 6). A detailed conformational analysis, combining H-1-NMR spectroscopy and molecular-mechanics computations, revealed that the four diastereoisomers displayed distinctly different conformational preferences (Figs. 2 and 3). These novel Cinchona-alkaloid analogs were quaternized to give (+)-(aS,3R,4S,8R,9S)-4, (+)-(aS,3R,4S,8S,9S)-5, (+)(aS,3R,4S,8R,9R)-6, and (-)-(aS,3R,4S,8S,9R)-7 (Scheme 7) which were tested as phase-transfer agents in the asymmetric allylation of phenylindanone 1. Without any optimization work, (+)-(aS,3R,4S,8R,9S)-4 was found to catalyze the allylation of 1 yielding the predicted enantiomer (+)-(S)-3b in 32% ee. The three diastereoisomeric catalysts (+)-5, (+)-6, and (-)-7 gave access to lower enantioselectivities (6 to 22% ee's), which could be rationalized by computer modeling (Fig. 4).

  DOI：

  10.1002/(sici)1522-2675(19990707)82:7<981::aid-hlca981>3.0.co;2-v

文献信息

• Asymmetric Phase-Transfer Catalysis by Quaternary Ammonium Ions Derived fromCinchona-Alkaloid Analogs Containing 1,1′-Binaphthalene Moieties
  作者：Laurent Ducry、François Diederich

  DOI：10.1002/(sici)1522-2675(19990707)82:7<981::aid-hlca981>3.0.co;2-v

  日期：1999.7.7

  The synthesis and catalytic properties of a new type of enantioselective phase-transfer catalysts, incorporating both the quinuclidinemethanol fragment of Cinchona alkaloids and a 1,1'-binaphthalene moiety, are described. Catalyst (+)-(aS,3R,4S,8R,9S)-4 with the quinuclidine fragment attached to C(7') in the major groove of the 1,1'-binaphthalene residue was predicted by computer modeling to be an efficient enantioselective catalyst for the unsymmetric alkylation of 6,7-dichloro-5-methoxy-2-phenylindanone (1; Scheme I, Fig. I). Its synthesis involved the selective oxidative cross-coupling of two differently substituted naphthalen-2-ols to afford the asymmetrically substituted 1,1'-binaphthalene derivative (+/-)-17 in high yield (Scheme 3). Chromatographic optical resolution via formation of diastereoisomeric camphorsulfonyl esters and functional-group manipulation gave access to the 7-bromo-1,1'-binaphthalene derivative (-)-(aS)-11 (Scheme 4). Nucleophilic addition of lithiated (-)-(aS)-11 to the quinuclidine Weinreb amide (+)-(3R,4S,8R)-8 afforded the two ketones (aS,3R,4S,8R)-27 and (aS,3R,4S,8S)-28 as an inseparable mixture of diastereoisomers (Scheme 6). Stereoselective reduction of this mixture with DIBAL-H (diisobutylaluminum hydride; preferred formation of the C(8)-C(9) erythro-pair of diastereoisomers with 18% de) or with NaBH4 (preferred formation of the threo-pair of diastereoisomers with 50% de) afforded the four separable diastereoisomers (+)-(aS,3R,4S,8S,9S)-29, (+)-(aS,3R,4S,8R,9R)-30, (-)-(aS,3R,4S,8S,9R)-31, and (+)-(aS,3R,4S,8R,9S)-32 (Scheme 6). A detailed conformational analysis, combining H-1-NMR spectroscopy and molecular-mechanics computations, revealed that the four diastereoisomers displayed distinctly different conformational preferences (Figs. 2 and 3). These novel Cinchona-alkaloid analogs were quaternized to give (+)-(aS,3R,4S,8R,9S)-4, (+)-(aS,3R,4S,8S,9S)-5, (+)(aS,3R,4S,8R,9R)-6, and (-)-(aS,3R,4S,8S,9R)-7 (Scheme 7) which were tested as phase-transfer agents in the asymmetric allylation of phenylindanone 1. Without any optimization work, (+)-(aS,3R,4S,8R,9S)-4 was found to catalyze the allylation of 1 yielding the predicted enantiomer (+)-(S)-3b in 32% ee. The three diastereoisomeric catalysts (+)-5, (+)-6, and (-)-7 gave access to lower enantioselectivities (6 to 22% ee's), which could be rationalized by computer modeling (Fig. 4).