2-cyclohexylidene-2-fluoroacetaldehyde | 66131-10-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-cyclohexylidene-2-fluoroacetaldehyde
• CAS: 66131-10-0
• 化学式: C₈H₁₁FO
• 分子量: 142.173
• InChiKey: KQSWALRQXAFLRU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-cyclohexylidene-2-fluoroacetaldehyde 、 lithium dimethylcuprate 以55%的产率得到
  参考文献：
  名称：

  CHUIT C.; SAUVETRE R.; MASURE D.; NORMANT J. F., TETRAHEDRON, 1979, 35, NO 22, 2645-2653

  摘要：

  DOI：
• 作为产物：
  描述：

  2-cyclohexylidene-2-fluoro-N-methoxy-N-methylacetamide 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 1.25h， 以63%的产率得到2-cyclohexylidene-2-fluoroacetaldehyde
  参考文献：
  名称：

  α-Fluorovinyl Weinreb Amides and α-Fluoroenones from a Common Fluorinated Building Block

  摘要：

  Synthesis and reactivity of N-methoxy-N-methyl-(1,3-benzothiazol-2-ylsulfonyl)fluoroacetamide, a building block for Julia olefination, is reported. This reagent undergoes condensation reactions with aldehydes and cyclic ketones to give alpha-fluorovinyl Weinreb amides. Olefination reactions proceed under mild, DBU-mediated conditions, or in the presence of NaH. DBU-mediated condensations proceed with either E- or Z-selectivity, depending upon reaction conditions, whereas NaH-mediated reactions are >= 98% Z-stereoselective. Conversion of the Weinreb amide moiety in N-methoxy-N-methyl-(1,3-benzothiazol-2-ylsulfanyl)fluoroacetamide to ketones, followed by oxidation, resulted in another set of olefination reagents, namely (1,3-benzothiazol-2-ylsulfonyl)fluoromethyl phenyl and propyl ketones. In the presence of DBU, these compounds react with aldehydes tested to give alpha-fluoroenones with high Z-selectivity. The use of N-methoxy-N-methyl-(1,3-benzothiazol-2-ylsulfanyl)fluoroacetamide as a common fluorinated intermediate in the synthesis of alpha-fluorovinyl Weinreb amides and alpha-fluoroenones has been demonstrated. Application of the Weinreb amide to alpha-flu-fluoro allyl amine synthesis is also shown.

  DOI：

  10.1021/jo802784w

文献信息

• Catalytic Domino Reaction of Ketones/Aldehydes with Me₃SiCF₂Br for the Synthesis of α-Fluoroenones/α-Fluoroenals
  作者：Xiaoning Song、Jian Chang、Dongsheng Zhu、Jiaheng Li、Cong Xu、Qun Liu、Mang Wang

  DOI：10.1021/acs.orglett.5b00488

  日期：2015.4.3

  α-fluoroenals is described to undergo the in situ formation of difluorocarbene and silyl enol ether, difluorocyclopropanation, desilylation, ring-opening, and defluorination sequence. In this tandem reaction, Me3SiCF2Br acts as not only the difluorocarbene source but also the TMS transfer agent as well as internal bromide and fluoride anion catalyst. It allows the transformations to occur smoothly under only

  可烯化的羰基化合物与Me 3 SiCF 2 Br的独特的多米诺反应，以构建α-氟烯和α-氟烯，被描述为原位形成二氟卡宾和甲硅烷基烯醇醚，二氟环丙烷化，甲硅烷基化，开环和脱氟序列。在该串联反应中，Me 3 SiCF 2 Br不仅充当二氟卡宾源，而且还充当TMS转移剂以及内部溴化物和氟化物阴离子催化剂。它允许仅在催化量的n -Bu 4 NBr作为引发剂的情况下平稳地进行转变。
• Réaction du diméthylcuprate de lithium avec les dérivés carbonylés α,β-insaturés α-fluorés et α-chlorés
  作者：C. Chuit、R. Sauvêitre、D. Masure、J.F. Normant

  DOI：10.1016/0040-4020(79)87045-3

  日期：——

  Depending on the nature of the halogen, α-fluoro- and α-chloro-α,β-unsaturated carbonyl compounds (whose reduction potentials are greater than − 2.4V) react in different ways with lithium dimethylcuprate. With α-fluoro derivatives, both 1,2- and 1,4-addition is observed, their ratios depend on the steric hindrance of the β-position. 1,4-Addition products are obtained from aldehydes and β-monosubstituted

  根据卤素的性质，α-氟代和α-氯代-α，β-不饱和羰基化合物（其还原电势大于-2.4V）以不同的方式与二甲基铜乙酸锂反应。对于α-氟衍生物，可以同时观察到1,2-和1,4-加成，它们的比例取决于β-位的空间位阻。从醛和β-单取代的α-氯代-α，β-烯键式酮和酯获得1,4-加成产物。β，β-二取代的α-氯代酮和酯只能通过卤素金属交换来还原卤素。
• 2-Fluoromethyl-4,4,6-trimetiiyl-1,3-oxasine as a new reagent for the preparation of α-fluoroaldehydes
  作者：Timothy B Patrick、Sedigheh Hosseini、Satinder Bains

  DOI：10.1016/s0040-4039(00)94364-8

  日期：1990.1
• Reduction of 1,1,2-Trifluoro-3-hydroxy-1-alkenes with Lithium Tetrahydroaluminate. A New Synthesis of 2-Fluoro-2-alkenals
  作者：R. SAUVÊTRE、D. MASURE、C. CHUIT、Jean F. NORMANT

  DOI：10.1055/s-1978-24684

  日期：——
• α-Fluorovinyl Weinreb Amides and α-Fluoroenones from a Common Fluorinated Building Block
  作者：Arun K. Ghosh、Shaibal Banerjee、Saikat Sinha、Soon Bang Kang、Barbara Zajc

  DOI：10.1021/jo802784w

  日期：2009.5.15

  Synthesis and reactivity of N-methoxy-N-methyl-(1,3-benzothiazol-2-ylsulfonyl)fluoroacetamide, a building block for Julia olefination, is reported. This reagent undergoes condensation reactions with aldehydes and cyclic ketones to give alpha-fluorovinyl Weinreb amides. Olefination reactions proceed under mild, DBU-mediated conditions, or in the presence of NaH. DBU-mediated condensations proceed with either E- or Z-selectivity, depending upon reaction conditions, whereas NaH-mediated reactions are >= 98% Z-stereoselective. Conversion of the Weinreb amide moiety in N-methoxy-N-methyl-(1,3-benzothiazol-2-ylsulfanyl)fluoroacetamide to ketones, followed by oxidation, resulted in another set of olefination reagents, namely (1,3-benzothiazol-2-ylsulfonyl)fluoromethyl phenyl and propyl ketones. In the presence of DBU, these compounds react with aldehydes tested to give alpha-fluoroenones with high Z-selectivity. The use of N-methoxy-N-methyl-(1,3-benzothiazol-2-ylsulfanyl)fluoroacetamide as a common fluorinated intermediate in the synthesis of alpha-fluorovinyl Weinreb amides and alpha-fluoroenones has been demonstrated. Application of the Weinreb amide to alpha-flu-fluoro allyl amine synthesis is also shown.