(R)-(-)-benzyl-α-d chloride | 4181-91-3

• 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: (R)-(-)-benzyl-α-d chloride
• 英文别名: (1R)-1-Deuteriobenzylchlorid；(R)-benzyl-α-d1 chloride；(S)-monodeuteriobenzyl chloride；((R)-chloro-deuterio-methyl)-benzene；[(R)-chloro(deuterio)methyl]benzene
• CAS: 4181-91-3
• 化学式: C₇H₇Cl
• 分子量: 127.578
• InChiKey: KCXMKQUNVWSEMD-MUFQJMLISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (R)-(-)-benzyl-α-d chloride 生成 (S)-(-)-(.alfa.-deuteriobenzyl)tributyltin
  参考文献：
  名称：

  LABADIE,*J. W.;STILLE, J. K., J. AMER. CHEM. SOC., 1983, 105, N 3, 669-670

  摘要：

  DOI：
• 作为产物：
  描述：

  α-phenyl-4-morpholineacetonitrile-α-d 在 盐酸 、 B-isopinocampheyl-9-borabicyclo[3.3.1]nonane 、 六氯丙酮 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 26.0h， 生成 (R)-(-)-benzyl-α-d chloride
  参考文献：
  名称：

  通过六氯丙酮/聚合物负载的三苯基膦从苯甲醇中手性氘代苄基氯：合成受保护的 (2S, 3S)-[3-2H,15N]-酪氨酸

  摘要：

  手性氘代苄基氯是使用新颖的、通用的六氯丙酮/聚合物负载的三苯基膦处理手性氘代苄醇制备的。双标记的受保护酪氨酸以 62% 的产率获得，α-碳为 86% de，β-碳为 82% de。合成的关键是 (15)N-标记的 (-)-8-苯基马尿酸与 R-(-)-4-三异丙基甲硅烷氧基苄基-α-d 氯化物的烷基化。

  DOI：

  10.1002/jlcr.3004

文献信息

• Stereoselective route to 15N-labeled-β-deuterated amino acids: synthesis of (2S,3R)-[3-2H,15N]-phenylalanine
  作者：Derek W. Barnett、Michael J. Panigot、Robert W. Curley

  DOI：10.1016/s0957-4166(02)00487-1

  日期：2002.9

  (2S,3R)-[3-2H,15N]-Phenylalanine hydrochloride was synthesized utilizing 15N-labeled 8-phenylmenthylhippurate as a chiral glycine equivalent. The key step in the synthesis was the alkylation of the glycine template with (S)-(+)-benzyl-α-d-mesylate. The doubly labeled alkylation product was obtained in 89% yield with 92% de at the α-carbon and 74% de at the β-carbon. The nature of the electrophile employed

  利用15 N-标记的8-苯基薄荷基马尿酸酯作为手性甘氨酸等效物，合成了（2 S，3 R）-[3- 2 H，15 N] -苯丙氨酸盐酸盐。合成的关键步骤是将甘氨酸模板与（S）-（+）-苄基-α-d-甲磺酸酯。获得双标记的烷基化产物，产率为89％，其中α-碳的de为92％，β-碳的de为74％。烷基化步骤中使用的亲电试剂的性质显着影响β-碳处的立体化学结果。在酸性条件下水解烷基化产物，然后从异丙醇中重结晶，得到标题化合物，为盐酸盐。通过NMR光谱法和HPLC分析最终产物的（-）-樟脑酰胺衍生物，发现α-碳上的de为76％，β-碳上的de为72％。所描述的合成策略代表了一种简单而通用的途径来制备手性氘代含氨基酸的β-亚甲基单元。
• The stereochemical course of fragmentation of benzyloxychlorocarbene
  作者：Robert A. Moss、Hong-Rak Kim

  DOI：10.1016/s0040-4039(00)97714-1

  日期：1990.1

  The fragmentation of α-deuteriobenzyloxychlorocarbene to α-deuteriobenzyl chloride in acetonitrile occurs with at least 60% net retention of stereochemistry.

  乙腈中的α-氘代苄氧基氯卡宾裂解为α-氘代苄基氯，其立体化学净保留率至少为60％。
• C(sp3)-N Bond-Forming Reductive Elimination of Amines: Reactions of Bisphosphine-Ligated Benzylpalladium(II) Diarylamido Complexes
  作者：Seth L. Marquard、Devon C. Rosenfeld、John F. Hartwig

  DOI：10.1002/anie.200904032

  日期：2010.1.18

  A rare event: The benzylpalladium amido complex 1 (Ar=napthyl) was used to study the mechanism of an unusual reductive elimination of amines (see scheme). The observed inversion of configuration is proposed to result from dissociation of the amido ligand, followed by nucleophilic attack on the benzylic carbon atom. binap=2,2′‐bis(diphenylphosphanyl)‐1,1′‐binaphthyl, dppf=1,1′‐bis(diphenylphosphanyl)ferrocene

  罕见的事件：使用苄基钯酰胺基络合物1（Ar =萘基）研究异常还原胺的机理（参见方案）。提出观察到的构型反转是由于酰胺配体解离，随后对苄基碳原子的亲核攻击所致。binap = 2,2'-双（二苯基膦基）-1,1'-联萘基，dppf = 1,1'-双（二苯基膦基）二茂铁。
• Mechanistic Aspects of the Reaction of Anionic Iron(0)-Olefin Complexes with Organic Halides. Detection and Characterization of Paramagnetic Organometallic Intermediates
  作者：Dale H. Hill、Masood A. Parvez、Ayusman Sen

  DOI：10.1021/ja00086a022

  日期：1994.4

  The scope and the mechanism of the reactions of [CpFe(COD)][Li(TMEDA) (Cp = C5H5-; COD = 1,5-cyclooctadiene; TMEDA = Me(2)NCH(2)CH(2)NMe(2)), 1, with a number of organic monohalides and geminal dihalides were investigated. With monohalides organic coupling products were observed, and, in:particular, the coupling and cross-coupling of benzyl and allyl halides were studied in detail. The addition of 1 equiv of benzyl halide to 1 in benzene resulted in the initial formation of [CpFe(COD)(CH(2)Ph)], 7. The predominant pathway involved an initial one-electron transfer from [CpFe(COD)](-) to PhCH(2)X to form PhCH(2)X*(-) and [CpFe(COD)]*. PhCH(2)X*(-) quickly disproportionated to form PhCH(2)* and X(-). The benzyl radical then added to [CpFe(COD)]*. Once formed [CpFe(COD)(CH(2)Ph)] reacted with TMEDA in a disproportionation reaction to form 0.5 equiv of the paramagnetic compound, [(TMEDA)Fe(CH(2)Ph)(2)], 3, and 0.5 equiv of FeCp(2). When additional benzyl (or allyl) halide was added, it reacted with [(TMEDA)Fe(CH(2)Ph)(2)] to form the coupled (or cross-coupled) product. This coupling reaction involved the intermediacy of benzyl (and allyl) radicals, and the experimental results were consistent with the product being formed by the coupling of two radicals in solution.
• Mechanisms of the palladium-catalyzed couplings of acid chlorides with organotin reagents
  作者：Jeff W. Labadie、J. K. Stille

  DOI：10.1021/ja00357a026

  日期：1983.9