(3R,4S,5R)-3,5-dimethylhept-1-en-4-ol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3R,4S,5R)-3,5-dimethylhept-1-en-4-ol
• 化学式: C₉H₁₈O
• 分子量: 142.241
• InChiKey: MVTVDAPLCOTIFV-IWSPIJDZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 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：

  (R)-methoxytrifluoromethylphenylacetyl chloride 、 (3R,4S,5R)-3,5-dimethylhept-1-en-4-ol 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 72.0h， 以46%的产率得到
  参考文献：
  名称：

  A convergent synthesis of the C(11)–C(25) fragment of the aglycone of avermectin A2b

  摘要：

  Oxidation of the mixture of products obtained by treatment of (S)-2-methylbutanal 8 with the E-but-2-enyldi-isopinocampheylborane prepared from (+)-pinene gave a mixture of homoallylic alcohols from which the major isomer 9 was isolated by chromatography. Oxidation with vanadylacetoacetate and tert-butyl hydroperoxide gave the epoxides 12 and 13, ratio 80 : 20. Following procedures developed in a synthesis of the model spiroacetal 19, 1,3-dithiane was alkylated, firstly using the epoxide 12, and then, after protection of the product 21 so obtained as its acetonide 23, using the epoxide 25, to give the 2,2-dialkylated 1,3-dithiane 25. Deprotection was accompanied by cyclisation to give the spiroacetal 28. Spiroacetal 29 was similarly prepared and taken through to the C(11)-C(25) fragment 38 of the aglycone of avermectin A(2b) 3. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00590-5
• 作为产物：
  描述：

  (S)-2-甲基丁醛 、 (-)-(E)-crotyldiisopinocamphenylborane 以93%的产率得到
  参考文献：
  名称：

  BROWN, H. C.;BHAT, K. S.;RANDAD, K. S., J. ORG. CHEM., 52,(1987) N 16, 3701-3702

  摘要：

  DOI：

文献信息

• Highly Selective Carbon-Carbon Bond Forming Reactions Mediated by Chromium(II) Reagents
  作者：Tamejiro Hiyama、Yoshitaka Okude、Keizo Kimura、Hitosi Nozaki

  DOI：10.1246/bcsj.55.561

  日期：1982.2

  to produce unisolable allylchromium species which add efficiently to aldehydes or ketones with high degree of stereo- and chemoselectivity. Particularly, high threo selectivity is observed in the reaction of aldehydes and 1-bromo-2-butene and is ascribed to a chair-like six-membered transition state. Simple reduction of allylic and benzylic halides produces biallyls and bibenzyls, while gem-dibromocyclopropanes

  低价铬试剂由氯化铬 (III) 和半摩尔氢化铝锂在四氢呋喃中生成。该试剂的行为类似于市售的无水氯化铬 (II)，并还原烯丙基卤化物以产生不可溶的烯丙基铬物质，该物质可有效地添加到醛或酮中，具有高度的立体选择性和化学选择性。特别是，在醛和 1-溴-2-丁烯的反应中观察到高苏选择性，这归因于椅子状六元过渡态。烯丙基和苄基卤化物的简单还原产生二烯丙基和联苄基，而偕二溴环丙烷以优异的产率提供相应的丙二烯。
• COMPOSITIONS AND METHODS FOR STEREOSELECTIVE ALDEHYDE ALLYLATION AND CROTYLATION
  申请人：KIM Hyunwoo

  公开号：US20120190875A1

  公开（公告）日：2012-07-26

  Compositions and methods for practical, stereoselective allylation and crotylation for aldehyde substrates are described. The compositions and methods comprise reagents for allylation and/or crotylation and acids. In some embodiments, the reagents and acids are pre-mixed.

  本发明描述了一种用于醛底物的实用、立体选择性的烯丙基化和丙烯基化的组合物和方法。该组合物和方法包括用于烯丙基化和/或丙烯基化的试剂和酸。在一些实施例中，试剂和酸是预混合的。
• Allylstannation
  作者：Alessandro Gambaro、Daniele Marton、Valerio Peruzzo、Giuseppe Tagliavini

  DOI：10.1016/s0022-328x(00)87430-6

  日期：1982.2

  obtained from the equilibrated mixtures obtained by redistribution between Bu3SnC4H7 (C4H7 = trans-, cis-crotyl and α-methylallyl group) and Bu2SnCl2. The reactions are characterized by a high degree of stereoselectivity, especially when bulky R groups are present. The complete allylic rearrangement and the stereoselectivity indicate that an exacyclic transition state is involved. Two stereochemically different

  2-丁烯基-氯-二-正丁基锡，以不同的反式/顺式比例与纯净的RCHO（R = CH 3，C 2 H 5，C 2 H 5（CH 3）CH，（CH 3）2 CH，C 6 H 5）在25℃下以高收率得到苏/赤-α-甲基烯丙基碳氢化合物的混合物。从通过在Bu 3 SnC 4 H 7（C 4 H 7 =反式，顺式）之间重新分布而获得的平衡混合物中获得了相同的混合物。-巴豆基和α-甲基烯丙基）和Bu 2 SnCl 2。该反应的特征在于高度的立体选择性，特别是当存在庞大的R基团时。完全的烯丙基重排和立体选择性表明涉及环外过渡态。两个立体化学上不同的过渡态分别导致两个非对映异构体，即对映体RS，SR和RR，SS中的苏-和邻-α-甲基-烯丙基甲醇。
• Hoffmann, Reinhard W.; Brinkmann, Heinrich; Frenking, Gernot, Chemische Berichte, 1990, vol. 123, # 12, p. 2387 - 2394
  作者：Hoffmann, Reinhard W.、Brinkmann, Heinrich、Frenking, Gernot

  DOI：——

  日期：——
• HOFFMANN, REINHARD W.;BRINKMANN, HEINRICH;FRENKING, GERNOT, CHEM. BER., 123,(1990) N2, C. 2387-2394
  作者：HOFFMANN, REINHARD W.、BRINKMANN, HEINRICH、FRENKING, GERNOT

  DOI：——

  日期：——