2-((S)-1-Phenyl-ethyl)-benzo[1,3,2]dioxaborole | 196212-80-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-((S)-1-Phenyl-ethyl)-benzo[1,3,2]dioxaborole
• 英文别名: 2-[(1S)-1-phenylethyl]-1,3,2-benzodioxaborole
• CAS: 196212-80-3
• 化学式: C₁₄H₁₃BO₂
• 分子量: 224.067
• InChiKey: DOVBZBBJVVJICI-NSHDSACASA-N

物化性质

• 沸点：
  317.3±35.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.29
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-((S)-1-Phenyl-ethyl)-benzo[1,3,2]dioxaborole 在 盐酸 、 lithium aluminium tetrahydride 、 正丁基锂 、 lithium chloride 、 辛可宁 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 乙醚 、 氯仿 、 水 为溶剂， 反应 14.0h， 生成 β-methylphenylalanine hydrochloride
  参考文献：
  名称：

  β-取代α-氨基酸衍生物不对称合成的无环立体选择性硼烷基化反应

  摘要：

  通过甘氨酸叔丁酯的席夫碱乙酸酯与手性非外消旋 B-反应，以 94% 至≥99% ee 和 66-98% ds 制备光学活性的顺式或反式 β-取代的-α-氨基酸衍生物在金鸡纳生物碱、辛可尼丁 (CdOH) 或辛可宁 (CnOH)、碱和氯化锂存在下的烷基-9-BBN 衍生物。

  DOI：

  10.1021/ja0298794
• 作为产物：
  描述：

  苯乙烯 、 儿萘酚硼烷 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 乙二醇二甲醚 为溶剂， 反应 4.0h， 生成 2-((S)-1-Phenyl-ethyl)-benzo[1,3,2]dioxaborole
  参考文献：
  名称：

  β-取代α-氨基酸衍生物不对称合成的无环立体选择性硼烷基化反应

  摘要：

  通过甘氨酸叔丁酯的席夫碱乙酸酯与手性非外消旋 B-反应，以 94% 至≥99% ee 和 66-98% ds 制备光学活性的顺式或反式 β-取代的-α-氨基酸衍生物在金鸡纳生物碱、辛可尼丁 (CdOH) 或辛可宁 (CnOH)、碱和氯化锂存在下的烷基-9-BBN 衍生物。

  DOI：

  10.1021/ja0298794

文献信息

• Rh(I)-Catalyzed Asymmetric Hydrosilylation and Hydroboration/Oxidation Reactions Using Berens Ligand
  作者：Carolina S. Marques、Anthony J. Burke

  DOI：10.1080/00397910802323106

  日期：2008.11.3

  ligand 2 was used in a number of Rh(I)-catalyzed asymmetric hydrosilylations of acetophenones under standard conditions, affording the corresponding 1-arylalcohols in ees up to 65%. Some novel Rh catalysts were generated in situ from the neutral precatalyst [Rh(µ-Cl)(COD)]2 and screened in the catalytic asymmetric hydroboration/oxidation of styrenes, gave enantioselectivities of up to 62%.

  摘要 Berens 配体 2 在标准条件下用于许多 Rh(I) 催化的苯乙酮不对称氢化硅烷化反应，在 ees 中提供了高达 65% 的相应 1-芳基醇。一些新型 Rh 催化剂由中性预催化剂 [Rh(μ-Cl)(COD)]2 原位生成，并在苯乙烯的催化不对称硼氢化/氧化中筛选，对映选择性高达 62%。
• Electrophilic amination of catecholboronate esters formed in the asymmetric hydroboration of vinylarenes
  作者：Frances I. Knight、John M. Brown、Dario Lazzari、Alfredo Ricci、A. John Blacker

  DOI：10.1016/s0040-4020(97)00722-9

  日期：1997.8

  (S)-(4-Methoxyphenyl)-ethyl-1,3,2-benzodioxaborole, (S)-1-(4-chlorophenyl)ethyl-1,3,2-benzodioxaborole and (S)-1-indanyl-1,3,2-benzodioxaborole. intermediates in the catalytic asymmetric hydroboration of 4-chloro-and 4-methoxystyrene, were isolated as pure oils in 75%, 84% and 49% yield respectively. For the first example, amination with N-chloromagnesio-N-methyl-O-trimethylsilhydroxylamine gave a mixture of (S)-1-(4-methoxyphenyl)-N-methylethylamine in 33% yield, 88% e.e. and (S)-1-(4-methoxyphenyl) ethanol in 31% yield, 86% e.e.. Related results were obtained in the other cases, and the steps of catalytic hydroboration and amination could be combined in a single sequence without isolation of the intermediate. Numerous variants were carried out in the amination procedure with only marginal improvements in chemoselectivity. An investigation of the mechanism was carried out using low temperature heteronuclear NMR on C-13-1-(S)-1-(4-chlorophenyl)ethyl-1,3,2-benzodioxaborole. The dual pathway is a result of an irreversible and unselective initial step. (C) 1997 Elsevier Science Ltd.
• Metal promoted asymmetry in the 1,2-diboroethylarene synthesis: diboration versus dihydroboration
  作者：Jesús Ramı́rez、Anna M. Segarra、Elena Fernández

  DOI：10.1016/j.tetasy.2005.02.016

  日期：2005.4

  Metal catalysed addition of diboranes to vinylarenes produces the desired 1,2-bis(boronate)ester and mono(boronate)esters as by-products. Their relative rate is a sensitive function between the nature of the catalytic system and the electronic effects of the substrate, that influences the mechanistic steps of the catalytic cycle. However, asymmetry is only induced as moderate enantiomeric excess values, providing an enantioface differentiation, between the bis- and mono(boronate)esters. Alternatively, the method based on the catalytic asymmetric dihydroboration/oxidation of alkynes as diphenyl acetylene can provide 1,2-diphenyl-1,2-ethanediol (hydrobenzoin) with a selectivity of 68% mainly as the erythro isomer. (c) 2005 Elsevier Ltd. All rights reserved.
• Acyclic Stereoselective Boron Alkylation Reactions for the Asymmetric Synthesis of β-Substituted α-Amino Acid Derivatives
  作者：Martin J. O'Donnell、Jeremy T. Cooper、Mary M. Mader

  DOI：10.1021/ja0298794

  日期：2003.3.1

  Optically active syn- or anti-β-substituted-α-amino acid derivatives are prepared in 94 to ≥99% ee and 66−98% ds by reaction of the Schiff base acetate of glycine tert-butyl ester with chiral, nonracemic B-alkyl-9-BBN derivatives in the presence of the Cinchona alkaloid, cinchonidine (CdOH) or cinchonine (CnOH), base, and lithium chloride.

  通过甘氨酸叔丁酯的席夫碱乙酸酯与手性非外消旋 B-反应，以 94% 至≥99% ee 和 66-98% ds 制备光学活性的顺式或反式 β-取代的-α-氨基酸衍生物在金鸡纳生物碱、辛可尼丁 (CdOH) 或辛可宁 (CnOH)、碱和氯化锂存在下的烷基-9-BBN 衍生物。