(S)-alpha-cyano-3-(4-fluorophenoxy)benzyl alcohol | 102916-91-6

• 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: (S)-alpha-cyano-3-(4-fluorophenoxy)benzyl alcohol
• 英文别名: (2S)-2-[3-(4-fluorophenoxy)phenyl]-2-hydroxyacetonitrile
• CAS: 102916-91-6
• 化学式: C₁₄H₁₀FNO₂
• 分子量: 243.237
• InChiKey: JOCMKNDJEFJITQ-CQSZACIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.17
• 重原子数：
  18.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  53.25
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (S)-alpha-cyano-3-(4-fluorophenoxy)benzyl alcohol 、 2,2-二甲基-3-(2-甲基-1-丙烯-1-基)环丙烷甲酰氯 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 生成 (1R,3R)-2,2-Dimethyl-3-(2-methyl-propenyl)-cyclopropanecarboxylic acid (S)-cyano-[3-(4-fluoro-phenoxy)-phenyl]-methyl ester 、 (1R,3R)-2,2-Dimethyl-3-(2-methyl-propenyl)-cyclopropanecarboxylic acid (R)-cyano-[3-(4-fluoro-phenoxy)-phenyl]-methyl ester 、 (1S,3R)-2,2-Dimethyl-3-(2-methyl-propenyl)-cyclopropanecarboxylic acid (R)-cyano-[3-(4-fluoro-phenoxy)-phenyl]-methyl ester 、 (1S,3R)-2,2-Dimethyl-3-(2-methyl-propenyl)-cyclopropanecarboxylic acid (S)-cyano-[3-(4-fluoro-phenoxy)-phenyl]-methyl ester
  参考文献：
  名称：

  One-pot synthesis of optically active cyanohydrin acetates from aldehydes via lipase-catalyzed kinetic resolution coupled with in situ formation and racemization of cyanohydrins

  摘要：

  A novel one-pot synthesis of optically active cyanohydrin acetates from aldehydes has been accomplished by lipase-catalyzed kinetic resolution coupled with in situ formation and racemization of cyanohydrins in an organic solvent. Racemic cyanohydrins 2, generated from aldehydes 1 and acetone cyanohydrin in diisopropyl ether under the catalysis of basic anion-exchange resin (OH- form), were acetylated stereoselectively by a lipase from Pseudomonas cepacia (Amano) with isopropenyl acetate as an acylating reagent. The (S)-isomer of 2 was preferentially acetylated by the lipase, while the unreacted (R)-isomer was continuously racemized through reversible transhydrocyanation catalyzed by the resin. These processes thus enabled one-stage conversion of various aldehydes 1a-n into the corresponding (S)-cyanohydrin acetates 3a-n with up to 94% ee in 63-100% conversion yields. The racemization of the optically active cyanohydrin 2e by Amberlite IRA-904 (OH- form) was found to be much faster than the enzymatic acetylation, confirming the effective second-order asymmetric transformation. Enzymatic deacetylation of (S)-cyanohydrin acetates in an organic solvent and the synthesis of optically active pyrethroids are also described.

  DOI：

  10.1021/jo00047a016
• 作为产物：
  描述：

  (S)-(+)-1-cyano-1-<3-(4-fluorophenoxy)phenyl>methyl acetate 在 乙醇 作用下， 以 异丙醚 为溶剂， 反应 6.0h， 生成 (S)-alpha-cyano-3-(4-fluorophenoxy)benzyl alcohol
  参考文献：
  名称：

  One-pot synthesis of optically active cyanohydrin acetates from aldehydes via lipase-catalyzed kinetic resolution coupled with in situ formation and racemization of cyanohydrins

  摘要：

  A novel one-pot synthesis of optically active cyanohydrin acetates from aldehydes has been accomplished by lipase-catalyzed kinetic resolution coupled with in situ formation and racemization of cyanohydrins in an organic solvent. Racemic cyanohydrins 2, generated from aldehydes 1 and acetone cyanohydrin in diisopropyl ether under the catalysis of basic anion-exchange resin (OH- form), were acetylated stereoselectively by a lipase from Pseudomonas cepacia (Amano) with isopropenyl acetate as an acylating reagent. The (S)-isomer of 2 was preferentially acetylated by the lipase, while the unreacted (R)-isomer was continuously racemized through reversible transhydrocyanation catalyzed by the resin. These processes thus enabled one-stage conversion of various aldehydes 1a-n into the corresponding (S)-cyanohydrin acetates 3a-n with up to 94% ee in 63-100% conversion yields. The racemization of the optically active cyanohydrin 2e by Amberlite IRA-904 (OH- form) was found to be much faster than the enzymatic acetylation, confirming the effective second-order asymmetric transformation. Enzymatic deacetylation of (S)-cyanohydrin acetates in an organic solvent and the synthesis of optically active pyrethroids are also described.

  DOI：

  10.1021/jo00047a016

文献信息

• process for the preparation of optically-active cyanomethyl esters
  申请人：E.I. DU PONT DE NEMOURS AND COMPANY

  公开号：EP0109681A2

  公开（公告）日：1984-05-30

  Stereoisomerically-enriched cyanomethyl esters are prepared by treating a non-symmetrical ketene or an alpha-chiral carboxylic acid halide or reactive derivative thereof with an optically-active alphahydroxynitrile. Certain optically-active optionally substituted S-alphacyano-3-phenoxybenzyl alcohol intermediates are prepared by treating the corresponding aldehyde of ketone with a source of hydrogen cyanide in the presence of a substantially water-immiscible, aprotic solvent and a cyclo(D-phenylalanyl-D-histidine) as a catalyst.

  通过将非对称酮或α-手性羧酸卤化物或其活性衍生物与具有光学活性的α-羟腈进行处理，可制备立体异构体富集的氰甲基酯。某些具有光学活性的任选取代的 S-alphacyano-3-苯氧基苄醇中间体的制备方法是：在基本上不溶于水的壬烷溶剂和作为催化剂的环(D-苯丙氨酰-D-组氨酸)存在下，用氰化氢源处理相应的酮醛。
• Cyanohydrination catalyst
  申请人：E.I. DU PONT DE NEMOURS AND COMPANY

  公开号：EP0135691A2

  公开（公告）日：1985-04-03

  A cyanohydrination catalyst for the preparation of al- phahydroxynitriles from aldehydes and ketones comprises a solid cyclo-(D-phenylalanyl-D-histidine) or cyclo-(L-phenylalanyl-L-histidine)-dipeptide having a non-crystalline or amorphous component.

  一种用于从醛和酮制备 al- phahydroxynitriles 的氰氢化催化剂包括固体环-(D-苯丙氨酰-D-组氨酸)或环-(L-苯丙氨酰-L-组氨酸)-二肽，其具有非结晶或无定形成分。
• Preparation of cyanomethyl esters
  申请人：E.I. DU PONT DE NEMOURS AND COMPANY

  公开号：EP0172380A2

  公开（公告）日：1986-02-26

  Cyanomethyl esters are prepared by reacting a carboxylic acid halide with an alpha-hydroxynitrile in the presence of a minor amount of water a molar excess of a hydrogen halide acceptor and a catalytic amount of a tertiary-aminopyridine or N-methylimidazole.

  在少量水、摩尔过量的卤化氢受体和催化量的叔氨基吡啶或 N-甲基咪唑存在下，通过羧酸卤化物与 α-羟腈反应制备氰甲基酯。
• Chiral cyanohydrination process
  申请人：E.I. DU PONT DE NEMOURS AND COMPANY

  公开号：EP0205782A1

  公开（公告）日：1986-12-30

  Chiral aromatic cyanohydrins are prepared by treating an aromatic aldehyde with cyanide ions in the presence of an inert, aprotic solvent and a chiral cyclo(phenylalanyl-histidine) and an alcohol. The technique is especially useful for reducing the induction period when starting-up the process, increase the rate of reaction and to produce a product of increased enantiomeric selectivity.

  手性芳香族氰醇是在惰性、非烷基溶剂和手性环（苯丙氨酰-组氨酸）及醇的存在下，用氰离子处理芳香醛而制备的。该技术尤其适用于缩短工艺启动时的诱导期、提高反应速率和生产对映体选择性更高的产品。
• Process for the preparation of a chiral aromatic cyanohydrin
  申请人：SHELL OIL COMPANY

  公开号：EP0209636A1

  公开（公告）日：1987-01-28

  Enantiomeric selectivity is increased in chiral cyanohydrin­ation of an aromatic aldehyde using a chiral cyclo(phenylalanyl­histidine) catalyst by treating the (recycle) aldehyde to remove cata­lyst poisons or impurities which adversely effect enantiomeric selectivity.

  在使用手性环(苯丙氨组氨酸)催化剂对芳香醛进行手性氰氢化反应时，可通过处理（回收）醛来去除对对映体选择性有不利影响的催化剂毒物或杂质，从而提高对映体选择性。