^（Eng.）Fenestranes and the flattening of tetrahedral carbon Bhaskar Rao Venepalli and William C. Agosta Chem. Rev.; 1987; 87(2) pp 399 - 410; DOI:10.1021/cr00078a007
^（Eng.）The first step in this reaction sequence is an adaptation of the Stork enamine alkylation reacting cyclopentanone with 3-bromo-1-butene through an imine derivative with pyrrolidine and forming a magnesium salt with ethyl magnesium bromide. The next step is a regular Stork enamine reaction followed by an aldol condensation forming the cyclohexenone ring. The final step is a photolytic [2+2]cycloaddition.
^（Eng.）Synthesis, X-ray Crystallography, and Computational Analysis of 1-Azafenestranes Scott E. Denmark, Justin I. Montgomery, and Laurenz A. Kramps J. Am. Chem. Soc.; 2006; 128(35) pp 11620 - 11630; (Article) DOI:10.1021/ja0632759
^（Eng.）In step 1 the alkyl halide 1-iodo-3-butene 1 is converted to a cyanozinc cuprate 2 (by transmetalation of the organozinc iodide with copper cyanide) which reacts in the next step with 1-nitro-cyclopentene 3 in a nucleophilic addition whereby the nitronate 4 is captured by phenylselenenyl bromide to the selenium intermediate 5. Hydrogen peroxide oxidation of 5 yields the nitroalkene 6 as a mixture of syn and anti isomers. A [4+2]cycloaddition with n-butyl-enol ether in presence of trimethyl aluminum gives the nitronate 7 and a second [3+2]cycloaddition by heating in presence of potassium carbonate gives the nitroso acetal 8. Hydrogenation with Raney nickel gives the diol 9 which on a double Mitsunobu reaction (with an amine proton donor) gives the azafenestrane 10 as the borane salt.
十月 31, 2023
窗烷, 是一种有机化合物, 属烷烃类, 其中心结构是由一个碳原子的四个共价键延伸出4个共边的碳氢环, 稠碳氢环, 状如窗户而得名, 可以看成是一类螺烷烃, 于1972年由化学家vlasios, georgian, 和martin, saltzman, 提出, 其英文名字fenestrane, 来自拉丁文的, 窗户, 从左至右为, 一般结构, 概要, 编辑正常情况下, 中心碳原子的sp3杂化导致其共价键呈正四面体结构, 的四环构型则需要这些共价键更倾向于平面结构, 因此不容易合成, 理论上, 最小的包含4个3员环, . 窗烷是一种有机化合物 属烷烃类 其中心结构是由一个碳原子的四个共价键延伸出4个共边的碳氢环 稠碳氢环 1 状如窗户而得名 可以看成是一类螺烷烃 于1972年由化学家Vlasios Georgian 和Martin Saltzman 2 提出 其英文名字Fenestrane 来自拉丁文的 窗户 窗烷 从左至右为 一般结构 4 4 4 4 窗烷 5 5 5 5 窗烷概要 编辑正常情况下 中心碳原子的sp3杂化导致其共价键呈正四面体结构 窗烷的四环构型则需要这些共价键更倾向于平面结构 因此不容易合成 理论上 最小的窗烷包含4个3员环 环丙烷 称为 3 3 3 3 窗烷 下一个成员 4 4 4 4 窗烷包含四个稠合的环丁烷体系 如同窗户一般 命名窗烷时 只需要将各环中碳原子数目数出 以逗号相隔 并用方括号括起来 后面接上 窗烷 就可以了 窗烷也有系统命名 如 4 4 4 4 窗烷的系统命名是 四环 3 3 1 03 9 07 9 壬烷 在某些极端情况下正四面体结构的碳彻底变成平面四边形结构 平面四边形甲烷的分子轨道图像表明 三个sp2杂化轨道中的两个轨道分别与两个氢原子成普通的s键 第三个杂化轨道与两个剩余的氢原子成三中心两电子键 仅利用两个氢的电子 而碳的两个未成对电子则被挤进垂直的p轨道 由于共振 四个碳氢键是完全等同的 电脑模拟表明完成这样的过程需要95 250kcal mol的能量 张力很大的 4 4 4 5 窗烷已被合成出来 X射线衍射表明中心碳原子键角大约为130 并且键长较短 149pm于普通的159pm 第一个合成的窗烷是 4 5 5 6 窗烷 3 nbsp 氮杂 4 5 5 5 窗烷也于最近被合成出来 以便结晶被X射线衍射分析 4 5 nbsp 氟硼酸盐中 N C C 键角为126 另見 编辑名稱獨特的化學物質列表参考资料 编辑 Eng Fenestranes and the flattening of tetrahedral carbon Bhaskar Rao Venepalli and William C Agosta Chem Rev 1987 87 2 pp 399 410 DOI 10 1021 cr00078a007 Eng Syntheses directed toward saturated flat carbon Vlasios Georgian Martin Saltzman Tetrahedron Letters Volume 13 Issue 42 1972 Pages 4315 4317 DOI 10 1016 S0040 4039 01 94304 7 Eng The first step in this reaction sequence is an adaptation of the Stork enamine alkylation reacting cyclopentanone with 3 bromo 1 butene through an imine derivative with pyrrolidine and forming a magnesium salt with ethyl magnesium bromide The next step is a regular Stork enamine reaction followed by an aldol condensation forming the cyclohexenone ring The final step is a photolytic 2 2 cycloaddition Eng Synthesis X ray Crystallography and Computational Analysis of 1 Azafenestranes Scott E Denmark Justin I Montgomery and Laurenz A Kramps J Am Chem Soc 2006 128 35 pp 11620 11630 Article DOI 10 1021 ja0632759 Eng In step 1 the alkyl halide 1 iodo 3 butene 1 is converted to a cyanozinc cuprate 2 by transmetalation of the organozinc iodide with copper cyanide which reacts in the next step with 1 nitro cyclopentene 3 in a nucleophilic addition whereby the nitronate 4 is captured by phenylselenenyl bromide to the selenium intermediate 5 Hydrogen peroxide oxidation of 5 yields the nitroalkene 6 as a mixture of syn and anti isomers A 4 2 cycloaddition with n butyl enol ether in presence of trimethyl aluminum gives the nitronate 7 and a second 3 2 cycloaddition by heating in presence of potassium carbonate gives the nitroso acetal 8 Hydrogenation with Raney nickel gives the diol 9 which on a double Mitsunobu reaction with an amine proton donor gives the azafenestrane 10 as the borane salt 取自 https zh wikipedia org w index php title 窗烷 amp oldid 60861614, 维基百科，wiki，书籍，书籍，图书馆，
