(methyl-3' butanal-1'-yl-3')-2 dithianne-1,3 | 86476-41-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二噻烷
• 英文名称: (methyl-3' butanal-1'-yl-3')-2 dithianne-1,3
• 英文别名: 3-(1,3-Dithian-2-yl)-3-methylbutan-1-al；3-(1,3-dithian-2-yl)-3-methylbutanal
• CAS: 86476-41-7
• 化学式: C₉H₁₆OS₂
• 分子量: 204.357
• InChiKey: DCLSKFQYYUJWFW-UHFFFAOYSA-N

物化性质

• 沸点：
  312.4±22.0 °C(predicted)
• 密度：
  1.101±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  67.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (methyl-3' butanal-1'-yl-3')-2 dithianne-1,3 在 水 、 sodium methylate 、 copper(l) cyanide 、 lithium 、 三乙胺 、 calcium carbonate 、 碘甲烷 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 52.5h， 生成 (Z)-4-(4-(triphenylsilyl)-2-oxodihydrofuran-3(2H)-ylidene)-2,2-dimethylbutanal
  参考文献：
  名称：

  SmI₂-Mediated Radical Cyclizations Directed by a C−Si Bond

  摘要：

  The use of a silicon stereocontrol element in cyclobutanol and cyclopentanol-forming cyclizations mediated by SmI2 results in excellent diastereocontrol. The C-Si bond in the products of cyclization provides a versatile handle for further manipulation. An asymmetric route to cyclization substrates involving copper-catalyzed silyl transfer has also been developed.

  DOI：

  10.1021/ol102278c
• 作为产物：
  描述：

  Alpha,Alpha-二甲基-γ-丁内酯 在 4 A molecular sieve 、 三氟化硼乙醚 、 三氧化硫吡啶 、 二异丁基氢化铝 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 8.0h， 生成 (methyl-3' butanal-1'-yl-3')-2 dithianne-1,3
  参考文献：
  名称：

  Samarium(II)-mediated 4-exo-trig cyclisations of unsaturated aldehydes. A stereoselective approach to functionalised cyclobutanols

  摘要：

  γ,δ-不饱和醛具有完全取代的中心，无论是在α-还是β-位置，均是通过取代的γ-丁内酯制备的，并在处理时与锶(II)碘化物发生高效的4-exo-trig环化反应，生成功能化的环丁醇。在所有情况下，环化反应都以完全的非对映选择性进行，生成反式环丁醇产物。产物的立体化学已通过NOE和X射线晶体学研究得到确认。在具有双键上第三个取代基的底物的环化反应中，位于环外的新形成的第三个立体中心实现了显著的控制。讨论了该第三个中心的立体选择性的来源及其对共溶剂的显著依赖性。

  DOI：

  10.1039/a909549g

文献信息

• Addition conjuguee de derives lithies de dithianne-1,3 aux aldehydes αβ ethyleniques
  作者：L. Wartski、M. El Bouz

  DOI：10.1016/0040-4020(82)80108-7

  日期：1982.1

  In order to synthesize γ carbonyl aldehydes which are interesting precursors in organic synthesis, we examine the action of masked acylanions, the lithiated derivatives from 1,3 dithiane 1a and 2-phenyl-1,3- dithiane on selected unsaturated aldehydes: crotonaldehyde 2, cinnamaldehyde 3 3-methyl butenal 4 and methacrolein 5. In THF 1a leads with the four aldehydes to allylic alcohols. However 1b gives

  为了合成有机合成中有趣的前驱体γ羰基醛，我们研究了掩蔽的乙腈，1,3二噻吩1a和2-苯基-1,3-二噻吩的锂化衍生物对选定的不饱和醛的作用：巴豆醛2，肉桂醛3 3-甲基丁醛4和甲基丙烯醛5。在THF 1a中，与四个醛一起生成烯丙基醇。但是1b给出由CC和CO的添加而产生的产品。使用THF-HMPA，我们显示CC添加通常得到增强。此外，在所有检查的情况下，CC和CO的添加均在动力学控制下进行：观察到的区域选择性可以通过底物和试剂结构以及锂-羰基化合物相互作用产生的排斥相互作用来解释。
• Samarium(II)-mediated 4-exo trig ketyl-olefin cyclisation of unsaturated aldehydes. A general, stereoselective synthesis of functionalised cyclobutanols
  作者：Derek Johnston、Catherine M. McCusker、David J. Procter

  DOI：10.1016/s0040-4039(99)00910-7

  日期：1999.6

  gamma,delta-Unsaturated aldehydes having a quaternary centre in either the a or beta-position, have been prepared from substituted gamma-butyrolactones and undergo efficient 4-exo-trig ketyl-olefin cyclisation on treatment with samarium(II) iodide to give functionalised cyclobutanols. In all cases cyclisation occurs with complete diastereocontrol to give anti-cyclobutanol products. In the cyclisation of substrate 4ab, significant stereochemical control is achieved at three contiguous chiral centres. Both unsaturated esters and vinyl sulfones have been employed as substrates in the reaction. (C) 1999 Elsevier Science Ltd. All rights reserved.
• WARTSKI, L.;EL, BOUZ, M., TETRAHEDRON, 1982, 38, N 22, 3285-3289
  作者：WARTSKI, L.、EL, BOUZ, M.

  DOI：——

  日期：——
• The Remarkable Effect of Cosolvent on a Samarium(II)-Mediated 4-<i>exo-trig</i> Cyclization:  Further Synthetic Studies on Pestalotiopsin A
  作者：David J. Edmonds、Kenneth W. Muir、David J. Procter

  DOI：10.1021/jo026827o

  日期：2003.4.1

  A samarium(II)-mediated 4-exo-trig cyclization in which a remote stereocenter serves to control the facial selectivity of the cyclization is described. The apparent coordination of a tert-butyldimethylsilyl ether to the samarium center appears to give rise to the selectivity. The remarkable effect of the cosolvent, 2,2,2-trifluoroethanol, on the cyclization of this substrate, is also discussed. A stereoselective synthesis of the general class of gamma,delta-unsaturated aldehyde cyclization substrate is reported, and the utility of the cyclization is demonstrated in an approach to the fully functionalized core of pestalotiopsin A.
• SmI₂-Mediated Radical Cyclizations Directed by a C−Si Bond
  作者：Hassan Y. Harb、Karl D. Collins、Jose V. Garcia Altur、Sue Bowker、Leonie Campbell、David J. Procter

  DOI：10.1021/ol102278c

  日期：2010.12.3

  The use of a silicon stereocontrol element in cyclobutanol and cyclopentanol-forming cyclizations mediated by SmI2 results in excellent diastereocontrol. The C-Si bond in the products of cyclization provides a versatile handle for further manipulation. An asymmetric route to cyclization substrates involving copper-catalyzed silyl transfer has also been developed.

表征谱图