(S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone | 169124-54-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone
• 英文别名: (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethylcyclohex-2-enone；(S)-4-tert-butyldimethyIsilyloxy-2-cyclohexenone；(4S)-4-[tert-butyl(dimethyl)silyl]oxy-2,6,6-trimethylcyclohex-2-en-1-one
• CAS: 169124-54-3
• 化学式: C₁₅H₂₈O₂Si
• 分子量: 268.472
• InChiKey: POOOTPCCECOICT-GFCCVEGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.32
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone 在 四丁基氟化铵 、 水 作用下， 以 四氢呋喃 、 乙酸乙酯 为溶剂， 反应 0.5h， 以92%的产率得到(S)-phorenol
  参考文献：
  名称：

  [EN] METHODS FOR SYNTHESIS OF CHIRAL INTERMEDIATES OF CAROTENOIDS, CAROTENOID ANALOGS, AND CAROTENOID DERIVATIVES
  [FR] PROCEDES PERMETTANT LA SYNTHESE D'INTERMEDIAIRES CHIRAUX DE CAROTENOIDES, D'ANALOGUES DE CAROTENOIDES ET DE DERIVES DE CAROTENOIDES

  摘要：

  公开号：

  WO2006039685A3
• 作为产物：
  描述：

  [(1S,4R)-4-hydroxy-3,5,5-trimethylcyclohex-2-en-1-yl] acetate 在 咪唑 、 重铬酸吡啶 、 potassium carbonate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 39.0h， 生成 (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone
  参考文献：
  名称：

  Lipase-catalyzed asymmetric synthesis of (R)- and (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone and their dihydro derivatives

  摘要：

  Racemic 4-hydroxy-2,6,6-trimethyl-2-cyclohexenon trans- and cis-2,6,6-trimethyl-2-cyclohexene-1,4-diols were prepared by reduction of 4-oxoisophorone with sodium borohydride-cerium chloride. Lipase (PS-30)-catalyzed kinetic resolution of (+/-)-cis-2,6,6-trimethyl-2-cyclohexene-1,4-diol with vinyl acetate led to (1R, 4S)-4-acetoxy-2,6, 6-trimethyl-2-cyclohexen-1-ol (81 %ee);and (1S, 4K)-1-acetoxy-2,6,6-trimethyl-2-cyclohexene-4-ol (92 %ee). Hydrolysis of the former monoacetate and recrytallization of the resulting material afforded enantiomerically pure (1R, 4S)-2,6,6-trimethyl-2-cyclohexene-1,4-diol. On the other hand, recrystallization of (1S, 4R) monoacetate itself provided an optically pure sample, which was then hydrolyzed to give (1S, 417)-2,6,6-trimethylcyclohexene-1,4-diol. Transformation of both diols into (S)- and (R)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone was conducted in two steps including silylation and oxidation. Catalytic hydrogenation of these (S)- and(R)-silyloxy enones dyer Raney nickel afforded the corresponding dihydro derivatives.

  DOI：

  10.1016/0957-4166(95)00159-m

文献信息

• Matched and mismatched pairings in B-secotaxane construction: a structure elucidation study
  作者：Imad Safir、José I. Candela Lena、Laure Finet、Nicolas Birlirakis、Siméon Arseniyadis

  DOI：10.1016/j.tetasy.2005.09.012

  日期：2005.10

  observed with the (10R)-epimer of 2 and 6 yielding little, if any, diastereoselectivity. The structures of B-secotaxanes were assigned on the basis of spatial proximity effects in the proton NMR spectrum. Assignment of the C10/C11 stereochemistry was made possible through conversion of the B-secotaxoid frameworks, derived from the matched and mismatched adducts, to the corresponding cyclic acetals. Configurational

  基本的B-seco紫杉烷骨架的合成是通过A环段（14 S）-1与C环段（10 S）和（10 R）-α-烷氧基有机锂试剂的C10-C11偶联实现的，在原位制备从2和6通过ñ丁基锂介导的金属转移。（14 S）-1与（10 S）-2和（10 S）-6的匹配反应显示出出色的非对映选择性，提供12和34分别作为单一异构体，因此可以方便地进入高度功能化的紫杉烷二萜骨架。在（10 R）-受体2和6处观察到明显的不匹配产生的非对映选择性极小（如果有的话）。根据质子NMR光谱中的空间邻近效应，确定了B-七萜烷的结构。通过将由匹配和不匹配的加合物衍生的B-类紫杉醇骨架转化为相应的环状缩醛，可以分配C10 / C11立体化学。在所有研究的案例中，都证实了α-烷氧基有机锂衍生物的构型稳定性。阐明这些加合物的结构对于通过分子内羟醛缩醛反应成功实现C1-C2键是至关重要的，因为事实上在这种情况下，在C10处含有β-MOM取代基的加合物是不利的。
• Precursors to Damascenone:  Synthesis and Hydrolysis of Isomeric 3,9-Dihydroxymegastigma-4,6,7-trienes
  作者：Carolyn J. Puglisi、Merran A. Daniel、Dimitra L. Capone、Gordon M. Elsey、Rolf H. Prager、Mark A. Sefton

  DOI：10.1021/jf050327p

  日期：2005.6.1

  series of four isomeric 3,9-dihydroxymegastigma-4,6,7-trienes, 8, has been prepared. The (3S,6R,9S) isomer of 8 proved to be identical to an isomer of this compound tentatively identified as an intermediate in the formation of damascenone from an allene triol. Each of the four isomers, when hydrolyzed independently of each other at pH 3.0 and 25 degrees C, produced product mixtures in which the major product was damascenone (1). Contrary to expectation, 3-hydroxydamascone (5) was not observed in any of the hydrolyses. Consequently, the mechanism of formation of damascenone proposed earlier requires modification. In each hydrolysis, the product mixtures showed the presence of a second isomer of 8, produced by epimerization during hydrolysis. Chiral analysis on a Cyclosil B column revealed that this epimerization was occurring at C-3 in each of the hydrolyses.
• [EN] METHODS FOR SYNTHESIS OF CHIRAL INTERMEDIATES OF CAROTENOIDS, CAROTENOID ANALOGS, AND CAROTENOID DERIVATIVES<br/>[FR] PROCEDES PERMETTANT LA SYNTHESE D'INTERMEDIAIRES CHIRAUX DE CAROTENOIDES, D'ANALOGUES DE CAROTENOIDES ET DE DERIVES DE CAROTENOIDES
  申请人：HAWAII BIOTECH INC

  公开号：WO2006039685A3

  公开（公告）日：2007-01-04
• Lipase-catalyzed asymmetric synthesis of (R)- and (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone and their dihydro derivatives
  作者：Akira Tanaka、Hiroshi Yamamoto、Takayuki Oritani

  DOI：10.1016/0957-4166(95)00159-m

  日期：1995.6

  Racemic 4-hydroxy-2,6,6-trimethyl-2-cyclohexenon trans- and cis-2,6,6-trimethyl-2-cyclohexene-1,4-diols were prepared by reduction of 4-oxoisophorone with sodium borohydride-cerium chloride. Lipase (PS-30)-catalyzed kinetic resolution of (+/-)-cis-2,6,6-trimethyl-2-cyclohexene-1,4-diol with vinyl acetate led to (1R, 4S)-4-acetoxy-2,6, 6-trimethyl-2-cyclohexen-1-ol (81 %ee);and (1S, 4K)-1-acetoxy-2,6,6-trimethyl-2-cyclohexene-4-ol (92 %ee). Hydrolysis of the former monoacetate and recrytallization of the resulting material afforded enantiomerically pure (1R, 4S)-2,6,6-trimethyl-2-cyclohexene-1,4-diol. On the other hand, recrystallization of (1S, 4R) monoacetate itself provided an optically pure sample, which was then hydrolyzed to give (1S, 417)-2,6,6-trimethylcyclohexene-1,4-diol. Transformation of both diols into (S)- and (R)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone was conducted in two steps including silylation and oxidation. Catalytic hydrogenation of these (S)- and(R)-silyloxy enones dyer Raney nickel afforded the corresponding dihydro derivatives.