(1S,4S,5S)-4-(3-Butenyl)-4,6,6-trimethylbicyclo<3.1.1>heptan-2-one | 149339-39-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,4S,5S)-4-(3-Butenyl)-4,6,6-trimethylbicyclo<3.1.1>heptan-2-one
• CAS: 149339-39-9
• 化学式: C₁₄H₂₂O
• 分子量: 206.328
• InChiKey: FLQXYFUQRHSVDS-QKCSRTOESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.59
• 重原子数：
  15.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (1S,4S,5S)-4-(3-Butenyl)-4,6,6-trimethylbicyclo<3.1.1>heptan-2-one 在 Zn(TMP)₂ 、 zinc dibromide 、 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 6.0h， 以81%的产率得到(1R,3aR,4R,6S,7aR)-1-(bromomethyl)-3a,5,5-trimethyloctahydro-7H-4,6-methanoinden-7-one
  参考文献：
  名称：

  烯丙基镍催化使酮的羰基脱氢和氧化环烯基化成为可能

  摘要：

  我们在此公开了使用烯丙基-镍催化的第一排过渡金属催化的羰基化合物的α，β-脱氢的第一份报告。这一发展克服了先前报道的烯丙基-钯催化氧化的几个限制，并进一步用于开发氧化环烯基化反应，该反应提供了使用未活化的酮和烯烃前体获得具有稠合、桥连和螺环系统的双环烯酮的途径。

  DOI：

  10.1021/jacs.9b02552
• 作为产物：
  描述：

  (+)-apoverbenone 在 copper(l) iodide 、 Celite 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 2.5h， 生成 (1S,4S,5S)-4-(3-Butenyl)-4,6,6-trimethylbicyclo<3.1.1>heptan-2-one
  参考文献：
  名称：

  Efficient synthesis of (1S,5S)-4-alkyl-6,6-dimethylbicyclo[3.1.1]hept-3-en-2-ones from (1R,5S)-(+)-nopinone and preparation of some chiral building blocks suitable for the asymmetric synthesis

  摘要：

  A general and convenient transformation of (1R,5S)-(+)-nopinone (1) into (1S,5S)-4-alkyl-6,6-dimethylbicyclo[3.1.1]hept-3-en-2-ones, i.e., (-)-verbenone (6a) as the simplest compound and its C(4)-alkyl homologs 6b-f, via (+)-apoverbenone (7) is developed and applied, starting with 6a,e, to the syntheses of (4R,5R)-1-acetoxy-4-isopropenyl-5-methyl-5-vinyl-1-cyclohexene (12a) and (4R,5S)- and (4R,5R)-1-acetoxy-5-(3-butenyl)-4-isopropenyl-5-methyl-1-cyclohexene (12b and 12c), in connection with a search for chiral building blocks suitable for the asymmetric synthesis. Preparation of 12a indicates the formal synthesis of the elemanoid sesquiterpenes (-)-beta-elemenone and (-)-eleman-8beta,12-olide.

  DOI：

  10.1021/jo00067a026

文献信息

• Zinc-mediated anionic cyclization of unstabilized ketone enolates with unactivated alkenes
  作者：Diego Olivieri、David Huang、Alexandra K. Bodnar、Shijin Yu、Timothy R. Newhouse

  DOI：10.1016/j.tet.2020.131417

  日期：2020.12

  We report herein general conditions for a zinc-mediated anionic cyclization of unstabilized ketone enolates. This anionic cyclization allows access to various carbocyclic architectures by utilizing abundant ketones and unactivated alkenes as precursors. The transformation is enabled by the use of Zn(TMP)2 as base and Zn(OTf)2 as an additive. The resulting alkylzinc species can be intercepted by electrophiles

  我们在此报告了不稳定的酮烯酸酯的锌介导的阴离子环化的一般条件。通过利用丰富的酮和未活化的烯烃作为前体，这种阴离子环化反应可以进入各种碳环结构。通过使用Zn（TMP）2作为碱和Zn（OTf）2作为添加剂可以实现转化。最终的烷基锌物质可被亲电体拦截，形成串联的C–X和C–O键。
• Palladium‐Catalyzed Carbonylative Difunctionalization of Unactivated Alkenes Initiated by Unstabilized Enolates
  作者：Pengpeng Zhang、Timothy R. Newhouse

  DOI：10.1002/anie.202307455

  日期：2023.9.25

  A palladium-catalyzed carbonylative difunctionalization of unactivated alkenes initiated by enolate nucleophiles is described. Synthetically useful 1,5-diketone products were smoothly transformed into highly substituted pyridines. The method tolerates a range of electrophiles and proceeds under an atmospheric pressure of CO.

  描述了由烯醇化亲核试剂引发的钯催化的未活化烯烃的羰基双官能化。可合成的1,5-二酮产品顺利转化为高度取代的吡啶。该方法可耐受一系列亲电试剂，并在 CO 大气压下进行。
• Nickel-Catalyzed Difunctionalization of Unactivated Alkenes Initiated by Unstabilized Enolates
  作者：David Huang、Diego Olivieri、Yang Sun、Pengpeng Zhang、Timothy R. Newhouse

  DOI：10.1021/jacs.9b09245

  日期：2019.10.16

  This report demonstrates the possibility of a nickel-catalyzed difunctionalization of unactivated alkenes initiated by an unstabilized enolate nucleophile. The process tolerates a diverse range of electrophiles, including aryl, heteroaryl, alkenyl, and amino electrophiles. An electron-deficient phosphine ligand and a tetrabutylammonium salt additive were crucial for promoting efficient vicinal difunctionalization.