(1S,2R,3S,4R)-3-(2,2-dimethylpropoxy)-2-ethenyloxy-4,7,7-trimethylbicyclo<2.2.1>-heptane | 130822-45-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1S,2R,3S,4R)-3-(2,2-dimethylpropoxy)-2-ethenyloxy-4,7,7-trimethylbicyclo<2.2.1>-heptane
• 英文别名: (1R,2S,3R,4S)-2-(2,2-dimethylpropoxy)-3-ethenoxy-1,7,7-trimethylbicyclo[2.2.1]heptane
• CAS: 130822-45-6
• 化学式: C₁₇H₃₀O₂
• 分子量: 266.424
• InChiKey: WIIUPVWXGJHSPK-WBOJAVRRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,2R,3S,4R)-3-(2,2-dimethylpropoxy)-2-ethenyloxy-4,7,7-trimethylbicyclo<2.2.1>-heptane 在 二异丙氧基二氯化钛 、 碳酸氢钠 作用下， 以 甲苯 为溶剂， 反应 38.67h， 生成 methyl (1S,3R,5S,6aS,9aR,9bR)-5-<(1S,2R,3S,4R)-3-(2,2-dimethylpropoxy)-4,7,7-trimethylbicyclo-<2.2.1>heptan-2-oxy>-9b-methylhexahydro-1H-isooxazolo<2,3,4-h><2,1>benzoxazine-1-carboxylate
  参考文献：
  名称：

  串联[4 + 2] / [3 + 2]-环加成。2.手性乙烯基醚的不对称诱导

  摘要：

  乙烯基醚可有效引发串联连接到α，β-不饱和酯双极性亲和剂的硝基烯烃的串联[4 + 2] / [3 + 2]-环加成反应。使用手性乙烯基醚6作为亲二烯体，硝基烯烃1和2经历高度选择性的串联环加成。所得到的亚硝基缩醛的氢解裂解产生了> 98％ee的α-羟基内酰胺（-）- 14和（-）- 21，手性助剂的回收率很高。可以看出，非对映异构体的高选择性源于对乙烯基醚的强烈内在偏爱以及助剂中固有的表面偏向。

  DOI：

  10.1016/s0040-4020(01)85599-x
• 作为产物：
  描述：

  (1R,2S,3R,4S)-(2-(2,2-dimethylpropoxy)-1,7,7-trimethylbicyclo<2.2.1>heptan-3-oxy)ethyne 在 Pd-BaSO₄ 喹啉 、 氢气 作用下， 以 正己烷 为溶剂， 以92%的产率得到(1S,2R,3S,4R)-3-(2,2-dimethylpropoxy)-2-ethenyloxy-4,7,7-trimethylbicyclo<2.2.1>-heptane
  参考文献：
  名称：

  串联[4 + 2] / [3 + 2]-环加成。2.手性乙烯基醚的不对称诱导

  摘要：

  乙烯基醚可有效引发串联连接到α，β-不饱和酯双极性亲和剂的硝基烯烃的串联[4 + 2] / [3 + 2]-环加成反应。使用手性乙烯基醚6作为亲二烯体，硝基烯烃1和2经历高度选择性的串联环加成。所得到的亚硝基缩醛的氢解裂解产生了> 98％ee的α-羟基内酰胺（-）- 14和（-）- 21，手性助剂的回收率很高。可以看出，非对映异构体的高选择性源于对乙烯基醚的强烈内在偏爱以及助剂中固有的表面偏向。

  DOI：

  10.1016/s0040-4020(01)85599-x

文献信息

• Versatile Syntheses of Alkynyl- and Substituted Alkynylcyclopropanes: 2-Alkoxyethynylcyclopropanes for the Anellation of Bicyclo[3.3.0]octane Fragments
  作者：Hans-Christian Militzer、Sten Schömenauer、Carola Otte、Carsten Puls、Jürgen Hain、Stefan Bräse、Armin de Meijere

  DOI：10.1055/s-1993-25988

  日期：——

  Enol ethers 1a-f are brominated at - 78° C and the resulting alkyl 1,2-dibromoethyl ethers are regioselectively coupled with propargyl-magnesium bromide to give 4-alkoxy-5-bromo-1-pentynes 2a-f, which are protected at the acetylenic terminus with a trimethylsilyl group. These 4-alkoxy-5-bromo-1-trimethylsilyl-1-pentynes 3a-f readily cyclize by γ-elimination to give trimethylsilyl protected 2-alkoxyethynylcyclopropanes 4a-f in excellent overall yields. Under appropriate conditions (E)-diastereomers (E)-4a-f can be prepared selectively. The diastereoselectivity of the bromine addition onto enantiomerically pure chiral enol ethers 1e and 1f, however, is 64% (for 2f) at best. 2-Alkoxy-1-trimethylsilylethynyl-cyclopropanes (E/Z)-4 can be deprotonated with LDA or butyllithium to give configurationally stable 1-lithio derivatives (E)-6, which are trapped by reactive electrophiles (protons, carbonyl compounds, tosyl halides) with retention of configuration on the three-membered ring. 2-Alkoxy-1-ethynylcyclopropanes 5 can be used to anellate a bicyclo[3.3.0]octane fragment onto a cycloalkene in a domino-type reaction sequence, as demonstrated by the Pauson-Khand cycloaddition of (E)-5c to norbornene (14) as well as deltacyclene (20), and subsequent interconversion to the tetracyclic and hexacyclic compounds anti/syn-19 and anti/syn-25/27 with a reasonable degree of diastereoselectivity.

  Enol醚1a-f在-78°C下进行溴化，生成的烷基1,2-二溴乙基醚经区域选择性偶联反应与炔丙基-镁溴反应，得到4-烷氧基-5-溴-1-戊炔2a-f，其在炔端用三甲基硅基保护。这些4-烷氧基-5-溴-1-三甲基硅基-1-戊炔3a-f通过γ-消除易于环化，以优异的总收率得到三甲基硅基保护的2-烷氧基乙炔基环丙烷4a-f。在适当条件下，可以选择性地制备(E)-4a-f。然而，溴对纯手性enol醚1e和1f的加成反应的立体选择性最多为64%（对于2f）。2-烷氧基-1-三甲基硅基乙炔基环丙烷(E/Z)-4可通过LDA或丁基锂去质子化，得到构型稳定的1-锂衍生物(E)-6，这些衍生物通过保留三元环的构型被活性亲电试剂（质子、羰基化合物、甲苯磺酰卤化物）捕获。2-烷氧基-1-乙炔基环丙烷5可用于将双环[3.3.0]辛烷片段通过多米诺式反应序列结合到环烯上，如通过(E)-5c与降冰片烯（14）以及δ环烯（20）的Pauson-Khand环加成反应，随后通过合理的立体选择性相互转化为四环和六环化合物anti/syn-19以及anti/syn-25/27所证明。
• Tandem inter [4+2]/intra [3+2]nitroalkene cycloadditions. 5. Origin of the Lewis acid dependent reversal of stereoselectivity
  作者：Scott E. Denmark、Mark E. Schnute、C. B. W. Senanayake

  DOI：10.1021/jo00059a044

  日期：1993.3

  The stereochemical course of the tandem [4 + 2]/[3 + 2] nitroalkene cycloaddition with chiral enol ethers has been shown to exhibit remarkable sensitivity to the nature of the Lewis acid promoter. Cycloadditions using (+)-camphor-derived vinyl ether 3 or (-)-trans-2-phenylcyclohexanol-derived vinyl ether 6 gave a predominance of the 1S hydroxy lactam 4 when promoted by Ti(O-i-Pr)2Cl2. The same vinyl ethers selectively produced the 1R hydroxy lactam 4 when promoted by MAPh. The (E)- and (Z)-1-propenyl ethers of (-)-trans-2-phenylcyclohexanol have been used to investigate the reversal of selectivity. Cycloadditions promoted by Ti(O-i-Pr)2Cl2 were found to be endo selective (12:1), while MAD and MAPh favored exo approach of the dienophile. High levels of asymmetric induction were observed in the endo mode of the cycloaddition for propenyl ethers (E)-13 and (Z)-13, 97.9% ee and 82.2% ee, respectively, but an erosion of selectivity occurred in the exo mode (72.2% ee) presumably through an s-cis enol ether conformation.
• Tandem inter [4+2]/intra [3+2] cycloadditions. 3. The stereochemical influence of the Lewis acid
  作者：Scott E. Denmark、Mark E. Schnute

  DOI：10.1021/jo00024a005

  日期：1991.11

  trans-2-Phenylcyclohexanol has been employed as a chiral auxiliary in the inter [4 + 2]/intra [3 + 2] tandem cycloaddition of nitroalkenes with chiral vinyl ethers. A novel reversal of selectivity between cycloadditions catalyzed by the Lewis acids Ti(O-i-Pr)2Cl2 and MAPh has been discovered.
• Tandem [4+2]/[3+2]-cycloadditions. 2. Asymmetric induction with a chiral vinyl ether
  作者：Scott E. Denmark、C.B.W. Senanayake、Ho Ginny-Dai

  DOI：10.1016/s0040-4020(01)85599-x

  日期：1990.1

  A tandem [4+2]/[3+2]-cycloaddition of nitroalkenes tethered to α,β-unsaturated ester dipolarophiles can be effectively triggered with a vinyl ether. Using the chiral vinyl ether 6 as the dienophile, nitroalkenes 1 and 2 undergo highly selective tandem cycloaddition. Hydrogenolytic cleavage of the resulting nitroso acetals produce α-hydroxy lactams (-)-14 and (-)-21 in >98% e.e. with excellent recovery

  乙烯基醚可有效引发串联连接到α，β-不饱和酯双极性亲和剂的硝基烯烃的串联[4 + 2] / [3 + 2]-环加成反应。使用手性乙烯基醚6作为亲二烯体，硝基烯烃1和2经历高度选择性的串联环加成。所得到的亚硝基缩醛的氢解裂解产生了> 98％ee的α-羟基内酰胺（-）- 14和（-）- 21，手性助剂的回收率很高。可以看出，非对映异构体的高选择性源于对乙烯基醚的强烈内在偏爱以及助剂中固有的表面偏向。