7,7-dimethoxy-2-methylene-heptanal | 940279-14-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 7,7-dimethoxy-2-methylene-heptanal
• CAS: 940279-14-1
• 化学式: C₁₀H₁₈O₃
• 分子量: 186.251
• InChiKey: BIUZSEPJRRJXKR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.92
• 重原子数：
  13.0
• 可旋转键数：
  8.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  7,7-dimethoxy-2-methylene-heptanal 在 sodium hydroxide 、 silver nitrate 作用下， 以 乙醇 为溶剂， 反应 1.0h， 生成 7,7-dimethoxy-2-methylene-heptanoic acid
  参考文献：
  名称：

  Highly Diastereoselective Synthesis of vicinal Quaternary and Tertiary Stereocenters Using the Iodo-aldol Cyclization

  摘要：

  The intramolecular iodo-aldol cyclization of alpha-substituted enoate aldehydes and ketones is described. Using prochiral starting materials, the reaction produces hetero- and carbocycles containing quaternary centers adjacent to secondary or tertiary centers. The reactions occur in good yields and are highly selective for the trans-products, having the hydroxyl and iodomethyl groups on opposite faces of the ring system.

  DOI：

  10.1021/ol070482k
• 作为产物：
  描述：

  N,N-二甲基氯烯亚胺 、 7,7-二甲氧基庚醛 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以99%的产率得到7,7-dimethoxy-2-methylene-heptanal
  参考文献：
  名称：

  Highly Diastereoselective Synthesis of vicinal Quaternary and Tertiary Stereocenters Using the Iodo-aldol Cyclization

  摘要：

  The intramolecular iodo-aldol cyclization of alpha-substituted enoate aldehydes and ketones is described. Using prochiral starting materials, the reaction produces hetero- and carbocycles containing quaternary centers adjacent to secondary or tertiary centers. The reactions occur in good yields and are highly selective for the trans-products, having the hydroxyl and iodomethyl groups on opposite faces of the ring system.

  DOI：

  10.1021/ol070482k

文献信息

• Intramolecular Chromium(II)-Catalyzed Pinacol Cross Coupling of 2-Methylene-α,ω-dicarbonyls
  作者：Ulrich Groth、Marc Jung、Till Vogel

  DOI：10.1055/s-2004-822895

  日期：——

  Using only 10% of CrCl2 as catalyst, manganese-powder as reducing agent and TMSCl as scavenger, 2-methylene-α,ω-di­aldehydes and -ketones can be coupled to form cyclic diols dia­stereoselectively. The diastereomeric excess strongly depends on the ring size and the substituents of the ω-carbonyl group. The greater the ring size the higher diastereoselectivities are observed. In all cases cis-diols are preferentially formed.

  仅使用CrCl2的10%作为催化剂、锰粉作为还原剂和TMSCl作为清除剂，2-亚甲基-α,ω-二醛和二酮可以立体选择性地耦合形成环状二醇。立体异构过量强烈依赖于环的大小和ω-羰基的取代基。环越大，观察到的立体选择性越高。在所有情况下，优先形成顺式二醇。
• Catalytic Intramolecular Conjugate Additions of Aldehyde-Derived Enamines to α,β-Unsaturated Esters
  作者：Zebediah C. Girvin、Philip P. Lampkin、Xinyu Liu、Samuel H. Gellman

  DOI：10.1021/acs.orglett.0c01666

  日期：2020.6.5

  enamines to α,β-unsaturated esters. Despite extensive prior exploration of conjugate additions of aldehyde-derived enamines, catalytic conjugate additions to unactivated enoate esters are unprecedented. Achieving enantioselective and diastereoselective six-membered ring formation requires the coordinated action of a chiral pyrrolidine, for nucleophilic activation of the aldehyde via enamine formation, and

  我们报告了一对已知的催化剂，使醛衍生的烯胺分子内共轭加成到 α,β-不饱和酯。尽管之前对醛衍生的烯胺的共轭加成进行了广泛的探索，但未活化的烯酸酯的催化共轭加成是前所未有的。实现对映选择性和非对映选择性六元环的形成需要手性吡咯烷的协调作用，用于通过烯胺形成亲核活化醛，以及氢键供体，用于烯酸酯的亲电活化。正确选择氢键供体对于化学选择性至关重要，这需要最大限度地减少来自高醛醇反应的竞争。从环庚烯六步合成 (−)-yohimbane 证明了效用。