2-fluoro-3-methyl-8-(trimethylsilyl)octa-1,6(Z)-dien-3-ol | 255845-20-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-fluoro-3-methyl-8-(trimethylsilyl)octa-1,6(Z)-dien-3-ol
• 英文别名: (6Z)-2-fluoro-3-methyl-8-trimethylsilylocta-1,6-dien-3-ol
• CAS: 255845-20-6
• 化学式: C₁₂H₂₃FOSi
• 分子量: 230.398
• InChiKey: XJWVFBQMAVOVCB-VURMDHGXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-fluoro-3-methyl-8-(trimethylsilyl)octa-1,6(Z)-dien-3-ol 在 吡啶 、 4-二甲氨基吡啶 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 97.67h， 生成 1-(1-methylcyclopropyl)-2-(ethoxycarbonyl)-4-fluoro-5-methyl-10-(trimethylsilyl)deca-4(Z),8(Z)-dien-1-one
  参考文献：
  名称：

  The Fluorine Atom as a Cation-Stabilizing Auxiliary in Biomimetic Polyene Cyclizations:  Total Synthesis of dl-Dammarenediol¹

  摘要：

  Dammarenediols I (1a) and II (1b) were prepared by an efficient nonenzymatic biomimetic polyene tetracyclization route. The cyclization substrate, pentaenol 3, contains a tetramethylallylic alcohol initiator, an allyltrimethylsilane terminating group, and a fluorine atom at pro-C-13 to serve as a cation-stabilizing (C-S) auxiliary controlling the regiochemistry of the C/D ring juncture. The synthesis of 3 employed lithium-halogen exchange to create alcohols 10 and 19. The Z-fluoroalkene in 3 was introduced stereoselectively via the Trost palladium-catalyzed alkylation of allylic acetate 11 (Z/E: 4.6/1). The cyclization of 3 was most efficient (62% isolated yield) when it was added as a dilute solution in dichloromethane to trifluoroacetic acid at -45 degrees C to afford tetracyclic fluoro diene 24 possessing the trans-anti-trans-anti-trans ring stereochemistry of the dammaranes. Replacement of the fluorine atom of 24 with hydrogen with complete retention of configuration was accomplished using the Ohsawa-Oishi reagent (Na/K alloy and crown ether). Wacker oxidation of the resulting hydrocarbon provided ketone 28, which after ketalization was ozonolyzed with a reductive workup to give the SP-alcohol 30. Ketal hydrolysis followed by Grignard reaction with isopentenylmagnesium bromide afforded the dammarenediols (1/3, 1a/1b).

  DOI：

  10.1021/jo991196s
• 作为产物：
  描述：

  (Z)-5-(trimethylsilyl)-3-penten-1-ol 在 吡啶 、 2,2'-联吡啶 、 溴 、 叔丁基锂 、 magnesium bromide ethyl etherate 、 三苯基膦 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 2.13h， 生成 2-fluoro-3-methyl-8-(trimethylsilyl)octa-1,6(Z)-dien-3-ol
  参考文献：
  名称：

  The Fluorine Atom as a Cation-Stabilizing Auxiliary in Biomimetic Polyene Cyclizations:  Total Synthesis of dl-Dammarenediol¹

  摘要：

  Dammarenediols I (1a) and II (1b) were prepared by an efficient nonenzymatic biomimetic polyene tetracyclization route. The cyclization substrate, pentaenol 3, contains a tetramethylallylic alcohol initiator, an allyltrimethylsilane terminating group, and a fluorine atom at pro-C-13 to serve as a cation-stabilizing (C-S) auxiliary controlling the regiochemistry of the C/D ring juncture. The synthesis of 3 employed lithium-halogen exchange to create alcohols 10 and 19. The Z-fluoroalkene in 3 was introduced stereoselectively via the Trost palladium-catalyzed alkylation of allylic acetate 11 (Z/E: 4.6/1). The cyclization of 3 was most efficient (62% isolated yield) when it was added as a dilute solution in dichloromethane to trifluoroacetic acid at -45 degrees C to afford tetracyclic fluoro diene 24 possessing the trans-anti-trans-anti-trans ring stereochemistry of the dammaranes. Replacement of the fluorine atom of 24 with hydrogen with complete retention of configuration was accomplished using the Ohsawa-Oishi reagent (Na/K alloy and crown ether). Wacker oxidation of the resulting hydrocarbon provided ketone 28, which after ketalization was ozonolyzed with a reductive workup to give the SP-alcohol 30. Ketal hydrolysis followed by Grignard reaction with isopentenylmagnesium bromide afforded the dammarenediols (1/3, 1a/1b).

  DOI：

  10.1021/jo991196s

文献信息

• An application of the trost reaction to the stereoselective synthesis of trans-tetrasubstituted fluoroalkenes
  作者：Paul V. Fish、S. Pulla Reddy、Cheol H. Lee、William S. Johnson

  DOI：10.1016/s0040-4039(00)74700-9

  日期：1992.12

  The coupling of beta-fluoroallylic acetates (1) with stabilised ester-enolates (3), in the presence of catalytic palladium(0), gave tetrasubstituted fluoroalkenes (2) in good yield and with generally satisfactory trans-stereoselectivity.
• The Fluorine Atom as a Cation-Stabilizing Auxiliary in Biomimetic Polyene Cyclizations:  Total Synthesis of <i>dl</i>-Dammarenediol¹
  作者：William S. Johnson、William R. Bartlett、Boris A. Czeskis、Arnaud Gautier、Cheol H. Lee、Rémy Lemoine、Eric J. Leopold、Gregory R. Luedtke、Katherine J. Bancroft

  DOI：10.1021/jo991196s

  日期：1999.12.1

  Dammarenediols I (1a) and II (1b) were prepared by an efficient nonenzymatic biomimetic polyene tetracyclization route. The cyclization substrate, pentaenol 3, contains a tetramethylallylic alcohol initiator, an allyltrimethylsilane terminating group, and a fluorine atom at pro-C-13 to serve as a cation-stabilizing (C-S) auxiliary controlling the regiochemistry of the C/D ring juncture. The synthesis of 3 employed lithium-halogen exchange to create alcohols 10 and 19. The Z-fluoroalkene in 3 was introduced stereoselectively via the Trost palladium-catalyzed alkylation of allylic acetate 11 (Z/E: 4.6/1). The cyclization of 3 was most efficient (62% isolated yield) when it was added as a dilute solution in dichloromethane to trifluoroacetic acid at -45 degrees C to afford tetracyclic fluoro diene 24 possessing the trans-anti-trans-anti-trans ring stereochemistry of the dammaranes. Replacement of the fluorine atom of 24 with hydrogen with complete retention of configuration was accomplished using the Ohsawa-Oishi reagent (Na/K alloy and crown ether). Wacker oxidation of the resulting hydrocarbon provided ketone 28, which after ketalization was ozonolyzed with a reductive workup to give the SP-alcohol 30. Ketal hydrolysis followed by Grignard reaction with isopentenylmagnesium bromide afforded the dammarenediols (1/3, 1a/1b).