trans-4-(Benzyloxy)-1-chloro-5-methyl-2-hexene | 120361-28-6

• 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: trans-4-(Benzyloxy)-1-chloro-5-methyl-2-hexene
• 英文别名: [(E)-6-chloro-2-methylhex-4-en-3-yl]oxymethylbenzene
• CAS: 120361-28-6
• 化学式: C₁₄H₁₉ClO
• 分子量: 238.757
• InChiKey: FFULBUKEMKROOB-RMKNXTFCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  trans-4-(Benzyloxy)-1-chloro-5-methyl-2-hexene 、 在 copper(I) iodide-lithium chloride 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 以92%的产率得到(3R^*,4S^*)-3-Benzyloxy-4-ethenyl-2-methyl-5-decene
  参考文献：
  名称：

  Copper-catalyzed reactions of organotitanium reagents. Highly SN2'- and anti-selective and diastereo- and chemoselective alkylation of allylic chlorides and phosphates

  摘要：

  Organotitanium reagents undergo Cu(I)-catalyzed S(N)2' substitution reactions with allylic chlorides and phosphates in a regio-, stereo-, and chemoselective manner: in the presence of Me3SiCl or Me3SiOSO2CF3, they undergo preferential conjugate addition to enones.

  DOI：

  10.1021/jo00019a001

文献信息

• Copper-catalyzed reactions of organotitanium reagents. Highly selective SN2′-allylation and conjugate addition
  作者：Masayuki Arai、Bruce H. Lipshutz、Eiichi Nakamura

  DOI：10.1016/0040-4020(92)80022-8

  日期：1992.7

  the presence of a catalytic amount of CuI·2LiCl, alkyltitanium (RTi(O-i-Pr)3) and titanate reagents (RnTi(O-i-Pr)5−nLi) undergo highly selective SN2′-alkylation reactions with allylic chlorides and allylic diethylphosphates in high yields. The regioselectivity of the reaction is as high as 99.8%. The reaction proceeds with excellent anti-stereoselectivity with respect to the nucleophile and the leaving

  在催化量的CuI·2LiCl存在下，烷基钛（RTi（Oi-Pr）3）和钛酸酯试剂（R n Ti（Oi-Pr）5−n Li）进行高度选择性的S N 2'-烷基化反应，烯丙基氯化物和烯丙基磷酸二乙酯的收率很高。反应的区域选择性高达99.8％。反应的进行具有优异的抗-stereoselectivity相对于亲核试剂和离去基团，表现出高的1,2-反-diastereoselectivity与δ手性烯丙基氯。催化铜试剂还是在Me 3存在下将烷基转移至烯酮的缓和剂氯化硅。烷基钛基催化试剂选择性地与烯丙基磷酸盐而不是与烯酮反应，而在硅活化剂的存在下，它优先与烯酮而不是与磷酸盐反应。Me 2 CuLi和TiCl（Oi-Pr）3的混合物的1 H NMR研究提供了有关试剂组成的信息。
• 1,2-Asymmetric induction in the SN2'-allylation of organocopper and organozinc reagents
  作者：Masayuki Arai、Takashi Kawasuji、Eiichi Nakamura

  DOI：10.1021/jo00071a022

  日期：1993.9

  The S(N)2'-selective reaction of organocopper or organozinc reagents with allylic chlorides having a chiral center at the delta-position proceeds with up to 100% diastereoselectivity. The observed 1,2-asymmetric induction conforms to pure steric control (Cram-Felkin-Anh model) even in cases where conventional chelation control may seem to operate, and the level of the selectivity was found to be much higher than those found for the additions of organometallics to structurally comparable alpha-substituted carbonyl compounds.
• Virtually complete diastereofacial selectivity in the SN2' allylation of organocopper reagents
  作者：Eiichi Nakamura、Kouichi Sekiya、Masayuki Arai、Satoshi Aoki

  DOI：10.1021/ja00190a068

  日期：1989.4