(4R,6R)-2-vinyl-4,6-dimethyl-1,3-dioxane | 107657-16-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: (4R,6R)-2-vinyl-4,6-dimethyl-1,3-dioxane
• 英文别名: (4R,6R)-4,6-dimethyl-2-vinyl-1,3-dioxane；(4R,6R)-4,6-dimethyl-2-ethenyl-1,3-dioxane；(4R,6R)-2-ethenyl-4,6-dimethyl-1,3-dioxane
• CAS: 107657-16-9
• 化学式: C₈H₁₄O₂
• 分子量: 142.198
• InChiKey: SNMZTSUCSDYFNN-RNFRBKRXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4R,6R)-2-vinyl-4,6-dimethyl-1,3-dioxane 在 双(乙腈)氯化钯(II) 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 22.0h， 生成 (2R,4R)-4-[(R)-1-(2-Benzyloxy-ethyl)-but-3-enyloxy]-pentan-2-ol
  参考文献：
  名称：

  Hosokawa, Takahiro; Shinohara, Toru; Ooka, Yoshiharu, Chemistry Letters, 1989, p. 2001 - 2004

  摘要：

  DOI：
• 作为产物：
  描述：

  (2R,4R)-pentanediol 、 丙烯醛 在 4 A molecular sieve 、 对甲苯磺酸 作用下， 以 乙醚 为溶剂， 反应 17.0h， 以84%的产率得到(4R,6R)-2-vinyl-4,6-dimethyl-1,3-dioxane
  参考文献：
  名称：

  有机金属试剂与同手性 β-酮缩醛的不对称加成

  摘要：

  检查了有机锂试剂羰基加成到 β-酮缩醛的非对映选择性。将 MeLi 添加到衍生自 Pd(II) 催化的苯基乙烯基酮与 (R,R)-2,4-戊二醇的 β-酮缩醛中，得到 (4R,6R)-4,6-二甲基-2-[( 2R)-2-羟基-2-苯基丙基]-1,3-二恶烷在 75% de 中。

  DOI：

  10.1246/bcsj.61.3380

文献信息

• Palladium(II)-catalyzed acetalization of terminal olefins bearing electron-withdrawing substituents with optically active diols
  作者：Takahiro Hosokawa、Toshiyuki Ohta、Satoshi Kanayama、Shunichi Murahashi

  DOI：10.1021/jo00385a021

  日期：1987.5
• Asymmetric Diels-Alder Reactions with .alpha.,.beta.-Unsaturated Acetals
  作者：Tarek Sammakia、Martin A. Berliner

  DOI：10.1021/jo00102a006

  日期：1994.11

  Chiral alpha,beta-unsaturated acetals derived from 2,4-pentanediol are shown to undergo Lewis acid promoted Diels-Alder reactions with good diastereoselectivity.
• Studies on the mechanism and origin of stereoselective opening of chiral dioxane acetals
  作者：Scott E. Denmark、Neil G. Almstead

  DOI：10.1021/ja00021a040

  日期：1991.10

  A systematic examination of the mechanism and origin of stereoselection in the reaction of dioxane acetals with allyltrimethylsilane was undertaken. Experimental tests for two limiting mechanisms, synchronous (S(N)2-like) and dissociative (S(N)1-like) substitution processes, were investigated. The meso 2,4,6-trisubstituted 1,3-dioxane acetals cis- and trans-1 provided an interesting opportunity to test the timing of bond breaking and making in the substitution reaction. The modest and C(2)-substituent-dependent selectivity excluded the possibility of a direct S(N)2-type attack on a complexed acetal. Further, the enol ethers 3 and 5 and acyclic acetal 7 were studied as precursors of the putative oxocarbenium ion intermediate in the dissociative limit. The weak and inverted selectivity observed with these substrates ruled out the intermediacy of the extended, separated ion in reactions of the cyclic acetals under similar conditions. A unified mechanistic scheme involving three distinct ion pairs is proposed to explain the dependence of allylation selectivity on structural and experimental variables. The three species are analogous to those proposed in the classic Winstein scheme: (1) an intimate ion pair, (2) an external ion pair, and (3) a separated ion. Each of these proposed intermediates has a different stereochemical profile and the ultimate outcome is a composite of those factors that balance the contribution of the different intermediates. The influence of C(2) substituent, acetal configuration, Lewis acid type and stoichiometry, allylsilane stoichiometry, concentration, solvent, and temperature were investigated and integrated in the proposed mechanistic scheme.
• HOSOKAWA, TAKAHIRO;SHINOHARA, TORU;OOKA, YOSHIHARU;MURAHASHI, SHUN-ICHI, CHEM. LETT.,(1989) N1, C. 2001-2004
  作者：HOSOKAWA, TAKAHIRO、SHINOHARA, TORU、OOKA, YOSHIHARU、MURAHASHI, SHUN-ICHI

  DOI：——

  日期：——
• HOSOKAWA TAKAHIRO; OHTA TOSHIYUKI; KANAYAMA SATOSHI; MURAHASHI SHUN-ICHI, J. ORG. CHEM., 52,(1987) N 9, 1758-1764
  作者：HOSOKAWA TAKAHIRO、 OHTA TOSHIYUKI、 KANAYAMA SATOSHI、 MURAHASHI SHUN-ICHI

  DOI：——

  日期：——