(+/-)-cis-2-Undecen-5-ol | 143687-58-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (+/-)-cis-2-Undecen-5-ol
• 英文别名: (Z)-undec-2-en-5-ol；undec-2-en-5-ol
• CAS: 143687-58-5
• 化学式: C₁₁H₂₂O
• 分子量: 170.295
• InChiKey: JEUIFTOTENBRNM-XQRVVYSFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  12
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  二氧化碳 、 (+/-)-cis-2-Undecen-5-ol 在 正丁基锂 、 碘 作用下， 生成 (+/-)-(3R*,5S*,1'R*)-5-hexyl-3-(1-iodoethyl)-2,6-dioxacyclohexanone 、 (+/-)-(3S*,5S*,1'S*)-5-hexyl-3-(1-iodoethyl)-2,6-dioxacyclohexanone
  参考文献：
  名称：

  Stereochemistry of the iodocarbonatation of cis- and trans-3-methyl-4-pentene-1,2-diols: the unusual formation of several anti iodo carbonates

  摘要：

  A study on the stereoselective preparation of a series of 3-methyl-4,5-epoxy alcohols as an entry to polypropionates was undertaken. Initially, the opening of cis and trans TIPS-protected 2,3-epoxy butanols by propynyldiethylalane showed an excellent regioselectivity favoring the monoprotected 1,2-diol products. The resulting propargylic alcohols were stereoselectively reduced to the cis and trans 1-[(triisopropylsilyl)oxy]-3-methyl-4-hexen-2-ols. Iodocarbonatation of these four isomeric homoallylic alcohols was carried out and the stereochemistry of the intermediate iodo carbonates established. Interestingly, a complete anti selectivity (>20:1 anti:syn) was observed when both the syn 3-methyl and cis double-bond geometry were present (3b, 10, and 20). The anti relative configuration for all of the iodo carbonates was established by NMR, and that of 5b was confirmed by X-ray crystallography. This study demonstrated that the relative stereochemistry of the hydroxyl and C(3) methyl groups in combination with the cis or trans geometry of the alkene exerts a significant effect on the stereochemical outcome of the iodocarbonatation reaction. Methanolysis of the iodo carbonates produced the desired 3-methyl-4,5-epoxy alcohols. The application of this chemistry to the reiterative synthesis of polypropionates was carried out with epoxy alcohol 4a (anti isomer), producing a new homologated epoxy alcohol, 22, with six contiguous stereocenters in a highly stereoselective manner.

  DOI：

  10.1021/jo00073a027
• 作为产物：
  描述：

  2-Undecyn-5-ol 在 Lindlar's catalyst 喹啉 、 氢气 作用下， 以 正己烷 为溶剂， 反应 6.0h， 以72%的产率得到(+/-)-cis-2-Undecen-5-ol
  参考文献：
  名称：

  Stereochemistry of the iodocarbonatation of cis- and trans-3-methyl-4-pentene-1,2-diols: the unusual formation of several anti iodo carbonates

  摘要：

  A study on the stereoselective preparation of a series of 3-methyl-4,5-epoxy alcohols as an entry to polypropionates was undertaken. Initially, the opening of cis and trans TIPS-protected 2,3-epoxy butanols by propynyldiethylalane showed an excellent regioselectivity favoring the monoprotected 1,2-diol products. The resulting propargylic alcohols were stereoselectively reduced to the cis and trans 1-[(triisopropylsilyl)oxy]-3-methyl-4-hexen-2-ols. Iodocarbonatation of these four isomeric homoallylic alcohols was carried out and the stereochemistry of the intermediate iodo carbonates established. Interestingly, a complete anti selectivity (>20:1 anti:syn) was observed when both the syn 3-methyl and cis double-bond geometry were present (3b, 10, and 20). The anti relative configuration for all of the iodo carbonates was established by NMR, and that of 5b was confirmed by X-ray crystallography. This study demonstrated that the relative stereochemistry of the hydroxyl and C(3) methyl groups in combination with the cis or trans geometry of the alkene exerts a significant effect on the stereochemical outcome of the iodocarbonatation reaction. Methanolysis of the iodo carbonates produced the desired 3-methyl-4,5-epoxy alcohols. The application of this chemistry to the reiterative synthesis of polypropionates was carried out with epoxy alcohol 4a (anti isomer), producing a new homologated epoxy alcohol, 22, with six contiguous stereocenters in a highly stereoselective manner.

  DOI：

  10.1021/jo00073a027

文献信息

• A Novel Preparation of Allylic Trichlorotins from α,α-Diisopropylhomoallylic Alcohols and Its Application to Carbonyl Allylations
  作者：Yoshiro Masuyama、Keisuke Saeki、Sachiko Horiguchi、Yasuhiko Kurusu

  DOI：10.1055/s-2001-18102

  日期：——

  α,α-Diisopropylhomoallylic alcohols react with tin(II) chloride and NCS in CH2Cl2 at -40 °C to -60 °C to produce allylic tins and diisopropyl ketone, and the allylic tins in situ cause nucleophilic addition to aldehydes to afford α-substituted homoallylic alcohols.

  α,α-二异丙基同烯醇在-40 °C到-60 °C的条件下与氯化亚锡和NCS在CH2Cl2中反应，生成烯丙基锡和二异丙基酮，而生成的烯丙基锡在原位导致对醛的亲核加成，获得α-取代的同烯醇。
• α-Regioselective carbonyl allylation by an allylic tin compound prepared from 1-bromobut-2-ene and tin(<scp>II</scp>) bromide at a nonpolar organic–aqueous interface
  作者：Yoshiro Masuyama、Masayuki Kishida、Yasuhiko Kurusu

  DOI：10.1039/c39950001405

  日期：——

  1-Bromobut-2-ene on a dichloromethane–water biphasic system at 25 °C causes α-regioselective addition to aldehydes with SnBr2 to produce 1-substituted pent-3-en-1-ols, and causes γ-regioselective addition to aldehydes with SnBr2–Bu4NBr to produce 1-substituted 2-methylbut-3-en-1-ols.

  在25°C的二氯甲烷-水双相系统上，1-溴丁-2-烯引起醛与SnBr 2的α-区域选择性加成，生成1-取代的戊-3-烯-1-醇，并引起γ-区域选择性加成。与SNBR醛2 -Bu 4 NBR，以产生1-取代2-甲基丁-3-烯-1-醇。
• B(C₆F₅)₃-Promoted Tandem Silylation and Intramolecular Hydrosilylation: Diastereoselective Synthesis of Oxasilinanes and Oxasilepanes
  作者：Roman Shchepin、Chunping Xu、Patrick Dussault

  DOI：10.1021/ol1018757

  日期：2010.11.5

  B(C6F5)(3) promotes regio- and stereoselective cyclizations of unsaturated alkoxysilanes to generate oxasilinanes and oxasilepanes. The same products are available directly from alkenols via tandem silylation and hydrosilylation.
• Stereochemistry of the iodocarbonatation of cis- and trans-3-methyl-4-pentene-1,2-diols: the unusual formation of several anti iodo carbonates
  作者：Raymond Tirado、Jose A. Prieto

  DOI：10.1021/jo00073a027

  日期：1993.10

  A study on the stereoselective preparation of a series of 3-methyl-4,5-epoxy alcohols as an entry to polypropionates was undertaken. Initially, the opening of cis and trans TIPS-protected 2,3-epoxy butanols by propynyldiethylalane showed an excellent regioselectivity favoring the monoprotected 1,2-diol products. The resulting propargylic alcohols were stereoselectively reduced to the cis and trans 1-[(triisopropylsilyl)oxy]-3-methyl-4-hexen-2-ols. Iodocarbonatation of these four isomeric homoallylic alcohols was carried out and the stereochemistry of the intermediate iodo carbonates established. Interestingly, a complete anti selectivity (>20:1 anti:syn) was observed when both the syn 3-methyl and cis double-bond geometry were present (3b, 10, and 20). The anti relative configuration for all of the iodo carbonates was established by NMR, and that of 5b was confirmed by X-ray crystallography. This study demonstrated that the relative stereochemistry of the hydroxyl and C(3) methyl groups in combination with the cis or trans geometry of the alkene exerts a significant effect on the stereochemical outcome of the iodocarbonatation reaction. Methanolysis of the iodo carbonates produced the desired 3-methyl-4,5-epoxy alcohols. The application of this chemistry to the reiterative synthesis of polypropionates was carried out with epoxy alcohol 4a (anti isomer), producing a new homologated epoxy alcohol, 22, with six contiguous stereocenters in a highly stereoselective manner.