(S)-(E)-(+)-4-Hydroxy-2-hexenenitrile | 130323-25-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-(E)-(+)-4-Hydroxy-2-hexenenitrile
• 英文别名: (S),(E)-4-Hydroxyhex-2-enenitrile；(E,4S)-4-hydroxyhex-2-enenitrile
• CAS: 130323-25-0
• 化学式: C₆H₉NO
• 分子量: 111.144
• InChiKey: ZVKMULORXYCVKT-YUDCMIJISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  44
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-(E)-(+)-4-Hydroxy-2-hexenenitrile 、 乙酸异丙烯酯 以24%的产率得到
  参考文献：
  名称：

  BURGESS, KEVIN;CASSIDY, JUANITA;HENDERSON, IAN, J. ORG. CHEM., 56,(1991) N, C. 2050-2058

  摘要：

  DOI：
• 作为产物：
  描述：

  (S)-(E)-(-)-1-(Tributylstannyl)-1-penten-3-ol 在 碘 作用下， 以 乙醚 为溶剂， 反应 0.91h， 生成 (S)-(E)-(+)-4-Hydroxy-2-hexenenitrile
  参考文献：
  名称：

  Catalytic Asymmetric Addition of Polyfunctional Dialkylzincs to .beta.-Stannylated and .beta.-Silylated Unsaturated Aldehydes

  摘要：

  The addition of functionalized dialkylzincs to readily available beta-stannylated or beta-silylated unsaturated aldehydes in the presence of a catalytic amount of (1R,2R)-1,2-bis(trifluorosulfonamido)cyclohexane (8 mol%) provides chiral allylic alcohols in good yields (60-90%) and excellent enantioselectivity (usually in the range of 85-95% ee). The synthetic utility of these allylic alcohols as chiral building blacks is demonstrated. The gamma-stannylated allylic alcohols were submitted to a Stille coupling leading to polyfunctional allylic alcohols and gamma-alkoxy enones. A treatment with CuCN in N-methylpyrrolidone at 130 degrees C provided chiral unsaturated gamma-hydroxy nitriles. Finally, the desilylation of the gamma-silylated alcohols gave chiral allylic alcohols having a terminal double bond. The catalytic asymmetric addition was found to show an important inverse temperature dependance. A mechanism for this addition is proposed.

  DOI：

  10.1021/jo00094a027

文献信息

• Asymmetric synthesis of 2-aminonorbornane-2-carboxylic acids by Diels-Alder reaction
  作者：Carlos Cativiela、Pilar López、José A. Mayoral

  DOI：10.1016/s0957-4166(00)86334-x

  日期：1990.1
• Optically active building blocks from the SPAC reaction: a completely asymmetric synthesis of (4S-cis)-5-(cyclohexylmethyl)-4-hydroxy-2-pyrrolidinone, a statine analog
  作者：Kevin Burgess、Juanita Cassidy、Ian Henderson

  DOI：10.1021/jo00006a017

  日期：1991.3

  Factors that govern chemical and optical yields of methyl gamma-hydroxy-alpha,beta-unsaturated esters 1 formed in reactions of optically active sulfinylacetates 2 with aldehydes (the ''SPAC'' reaction) are defined. Racemic samples of these chirons (1) can be resolved via acylations mediated by crude preparations of the lipase Pseudomonas K-10 in organic solvents. Combinations of asymmetric SPAC reactions with these biocatalytic resolutions provide routes to highly optically active esters 1 in good yields. This methodology is applied in a completely asymmetric synthesis of (4S-cis)-5-(cyclohexylmethyl)-4-hydroxy-2-pyrrolidinone (15), a cyclic derivative of (3S,4S)-4-amino-5-cyclohexyl-3-hydroxypentanoic acid (ACHPA).
• BURGESS, KEVIN;CASSIDY, JUANITA;HENDERSON, IAN, J. ORG. CHEM., 56,(1991) N, C. 2050-2058
  作者：BURGESS, KEVIN、CASSIDY, JUANITA、HENDERSON, IAN

  DOI：——

  日期：——
• Ostwald Roswitha, Chavant Pierre-Yves, Stadtmueller Heinz, Knochel Paul, J. Org. Chem., 59 (1994) N 15, S 4143-4153
  作者：Ostwald Roswitha, Chavant Pierre-Yves, Stadtmueller Heinz, Knochel Paul

  DOI：——

  日期：——
• Catalytic Asymmetric Addition of Polyfunctional Dialkylzincs to .beta.-Stannylated and .beta.-Silylated Unsaturated Aldehydes
  作者：Roswitha Ostwald、Pierre-Yves Chavant、Heinz Stadtmueller、Paul Knochel

  DOI：10.1021/jo00094a027

  日期：1994.7

  The addition of functionalized dialkylzincs to readily available beta-stannylated or beta-silylated unsaturated aldehydes in the presence of a catalytic amount of (1R,2R)-1,2-bis(trifluorosulfonamido)cyclohexane (8 mol%) provides chiral allylic alcohols in good yields (60-90%) and excellent enantioselectivity (usually in the range of 85-95% ee). The synthetic utility of these allylic alcohols as chiral building blacks is demonstrated. The gamma-stannylated allylic alcohols were submitted to a Stille coupling leading to polyfunctional allylic alcohols and gamma-alkoxy enones. A treatment with CuCN in N-methylpyrrolidone at 130 degrees C provided chiral unsaturated gamma-hydroxy nitriles. Finally, the desilylation of the gamma-silylated alcohols gave chiral allylic alcohols having a terminal double bond. The catalytic asymmetric addition was found to show an important inverse temperature dependance. A mechanism for this addition is proposed.