(S)-1-phenylhex-4-yn-3-ol | 1189125-30-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S)-1-phenylhex-4-yn-3-ol
• 英文别名: (S)-1-phenyl-4-hexyn-3-ol；(3S)-1-phenylhex-4-yn-3-ol
• CAS: 1189125-30-1
• 化学式: C₁₂H₁₄O
• 分子量: 174.243
• InChiKey: CPXWNTYACJOKQA-GFCCVEGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  (S)-1-phenylhex-4-yn-3-ol 在 吡啶 、 咪唑 、 喹啉 、 4-二甲氨基吡啶 、 Pd-BaSO₄ 、 四丁基氟化铵 、 氢气 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 10.0~20.0 ℃ 、101.33 kPa 条件下， 反应 22.0h， 生成 diethyl (S)-(Z)-(6-phenyl-2-hexen-4-yl) phosphate
  参考文献：
  名称：

  通过铜催化的烯丙基烷基化将区域烷基和立体控制的仲烷基引入缺电子的芳烃

  摘要：

  铜催化的唑类，吡啶N-氧化物和氟代芳烃与仲烯丙基磷酸的烯丙基烷基化反应在温和的反应条件下以优异的γ- E选择性进行。与对映体富集的烯丙基磷酸酯的反应以1,3-抗立体选择性进行，以在芳环的α位生成烯丙基立体异构中心。

  DOI：

  10.1002/anie.201200809
• 作为产物：
  描述：

  1-苯基-4-己炔-3-酮 在 Noyori's catalyst 、 异丙醇 作用下， 以100%的产率得到(S)-1-phenylhex-4-yn-3-ol
  参考文献：
  名称：

  Formation of Chiral C(sp³)−C(sp) Bond by Allylic Substitution of Secondary Allylic Picolinates and Alkynyl Copper Reagents

  摘要：

  To establish allylic substitution of secondary allylic alcohol derivatives with alkynyl copper reagents, allylic esters bearing the (2-pyridine)CO2-, (2-pyrazine)CO2-, (EtO)(2)PO2-, C6F5CO2-, o-(Ph2P)-C6H4CO2-, MeOCO2-, or AcO-group were examined. First, picolinate (R-1 = Me, R-2 = CH2OPMB) was subjected to reaction with (TMS-C C)(2)CuLi center dot LiBr at 0 degrees C. Although no substitution took place, MgBr, (3 equiv) was found to promote the reaction to produce the anti S(N)2' product in 93% yield with 94% regioselectivity and 99% chirality transfer. In contrast, substitution of the other esters with the copper reagent in the presence of MgBr, were less reactive ((2-pyrazin)CO2-) or marginally reactive (other cases). Generality of the substitution using picolinates was established with five picolinates (R-1 = Me, Ph(CH2)(2), PMBO(CH2)(3); R-2 = Me, CH2OPMB, CH2OTBS, C5H11, c-C6H11) and seven alkynyl copper reagents (R-3 = TMS, Ph, p-TBSOC6H4, p- and o-MeOC6H4, P-MeC6H4, p-FC6H4), furnishing anti S(N)2' products in 61-93% yields with high regioselectivity (usually > 90%) and high chirality transfer (usually > 95%). In addition, transformation of the products was briefly studied.

  DOI：

  10.1021/jo901728b

文献信息

• Total Synthesis of (−)-Virginiamycin M2
  作者：Jie Wu、James S. Panek

  DOI：10.1002/anie.201002220

  日期：2010.8.16

  Has a nice ring to it: A concise and modular total synthesis of the naturally occurring antibiotic virginiamycin M2 is described. A Barbier‐type cyclization was used to close the 23‐membered macrocycle and deliver virginiamycin M2 in 19 steps from a chiral organosilane.

  有一个不错的指环：描述了天然抗生素维吉尼亚霉素M 2的简明和模块化的全合成。Barbier型环化反应用于封闭23个成员的大环化合物，并从手性有机硅烷中分19步递送维吉尼亚霉素M 2。
• Total Synthesis of (−)-Virginiamycin M₂: Application of Crotylsilanes Accessed by Enantioselective Rh(II) or Cu(I) Promoted Carbenoid Si–H Insertion
  作者：Jie Wu、James S. Panek

  DOI：10.1021/jo202119p

  日期：2011.12.16

  A stereoselective synthesis of the antibiotic (−)-virginiamycin M2 is detailed. A convergent strategy was utilized that proceeded in 10 steps (longest linear sequence) from enantioenriched silane (S)-15. This reagent, which was prepared via a Rh(II)- or Cu(I)-catalyzed carbenoid Si–H insertion, was used to introduce the desired olefin geometry and stereocenters of the C1–C5 propionate subunit. A modified

  详细介绍了抗生素（-）-维吉尼亚霉素M 2的立体选择性合成。从10个步骤（最长的线性顺序）中使用了对映体富集硅烷（S）-15的收敛策略。该试剂是通过Rh（II）或Cu（I）催化的类胡萝卜素Si-H插入制备的，用于引入所需的烯烃几何形状和C1-C5丙酸酯亚基的立体中心。改良的Negishi交叉偶联或有效的醇盐定向的钛介导的炔烃-炔烃还原偶联策略用于组装三取代的（E，E）-二烯。未充分利用的后期SmI 2介导的大环化被用于构建天然产物的23元大环支架。
• Formation of Chiral C(sp³)−C(sp) Bond by Allylic Substitution of Secondary Allylic Picolinates and Alkynyl Copper Reagents
  作者：Yohei Kiyotsuka、Yuichi Kobayashi

  DOI：10.1021/jo901728b

  日期：2009.10.2

  To establish allylic substitution of secondary allylic alcohol derivatives with alkynyl copper reagents, allylic esters bearing the (2-pyridine)CO2-, (2-pyrazine)CO2-, (EtO)(2)PO2-, C6F5CO2-, o-(Ph2P)-C6H4CO2-, MeOCO2-, or AcO-group were examined. First, picolinate (R-1 = Me, R-2 = CH2OPMB) was subjected to reaction with (TMS-C C)(2)CuLi center dot LiBr at 0 degrees C. Although no substitution took place, MgBr, (3 equiv) was found to promote the reaction to produce the anti S(N)2' product in 93% yield with 94% regioselectivity and 99% chirality transfer. In contrast, substitution of the other esters with the copper reagent in the presence of MgBr, were less reactive ((2-pyrazin)CO2-) or marginally reactive (other cases). Generality of the substitution using picolinates was established with five picolinates (R-1 = Me, Ph(CH2)(2), PMBO(CH2)(3); R-2 = Me, CH2OPMB, CH2OTBS, C5H11, c-C6H11) and seven alkynyl copper reagents (R-3 = TMS, Ph, p-TBSOC6H4, p- and o-MeOC6H4, P-MeC6H4, p-FC6H4), furnishing anti S(N)2' products in 61-93% yields with high regioselectivity (usually > 90%) and high chirality transfer (usually > 95%). In addition, transformation of the products was briefly studied.
• Regio- and Stereocontrolled Introduction of Secondary Alkyl Groups to Electron-Deficient Arenes through Copper-Catalyzed Allylic Alkylation
  作者：Yusuke Makida、Hirohisa Ohmiya、Masaya Sawamura

  DOI：10.1002/anie.201200809

  日期：2012.4.23

  Copper‐catalyzed allylic alkylation of azoles, a pyridine N‐oxide, and fluoroarenes with secondary allylic phosphates proceeded under mild reaction conditions with excellent γ‐E‐selectivity. The reactions with enantioenriched allylic phosphates proceeded with 1,3‐anti stereoselectivity to generate an allylic stereogenic center at the position α to the aromatic ring.

  铜催化的唑类，吡啶N-氧化物和氟代芳烃与仲烯丙基磷酸的烯丙基烷基化反应在温和的反应条件下以优异的γ- E选择性进行。与对映体富集的烯丙基磷酸酯的反应以1,3-抗立体选择性进行，以在芳环的α位生成烯丙基立体异构中心。
• Reversible 1,3-<i>anti</i>/<i>syn</i>-Stereochemical Courses in Copper-Catalyzed γ-Selective Allyl–Alkyl Coupling between Chiral Allylic Phosphates and Alkylboranes
  作者：Kazunori Nagao、Umi Yokobori、Yusuke Makida、Hirohisa Ohmiya、Masaya Sawamura

  DOI：10.1021/ja302520h

  日期：2012.5.30

  The stereochemical courses of the copper-catalyzed allyl-alkyl coupling between enantioenriched chiral allylic phosphates and alkylboranes were switchable between 1,3-anti and 1,3-syn selectivities by the choice of solvents and achiral alkoxide bases with different steric demands. The reactions with gamma-silylated allylic phosphates allow efficient synthesis of enantioenriched chiral allylsilanes with tertiary or quaternary carbon stereogenic centers. Cyclic and acyclic bimodal participation of alkoxyborane species in an organocopper addition-elimination sequence is proposed to account for the phenomenon of the anti/syn-stereochemical reversal.