1,1,1,3,3,3-hexadeuterio-2-propylmagnesium bromide | 99727-83-0

• 分子结构分类: 有机化合物 - 有机金属化合物
• 英文名称: 1,1,1,3,3,3-hexadeuterio-2-propylmagnesium bromide
• 英文别名: (propan-2-yl-1,1,1,3,3,3-d6)magnesium bromide；isopropylmagnesium bromide
• CAS: 99727-83-0
• 化学式: C₃H₇BrMg
• 分子量: 153.25
• InChiKey: UCJIVFREPMUZDC-ADBWCSELSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.83
• 重原子数：
  5.0
• 可旋转键数：
  3.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  1,1,1,3,3,3-hexadeuterio-2-propylmagnesium bromide 生成 2,3-Dimethyl-<1,1,1,4,4,4-D6>-butan
  参考文献：
  名称：

  RILATT, J. A.;KITCHING, W., ORGANOMETALLICS, 1982, 1, N 8, 1089-1093

  摘要：

  DOI：
• 作为产物：
  描述：

  2-溴丙烷-D6 在 magnesium 作用下， 以 乙醚 为溶剂， 反应 0.5h， 生成 1,1,1,3,3,3-hexadeuterio-2-propylmagnesium bromide
  参考文献：
  名称：

  钛催化酯与脂肪族有机镁化合物环丙烷化的机理。四异丙醇钛存在下(CD3)2CHMgBr与3-氯丙酸乙酯反应产物中氘的分布

  摘要：

  (CD3)2CHMgBr 与 3-氯丙酸乙酯在催化量的 Ti(OPr)4 存在下反应生成 (E)-1-(2-氯乙基)-3,3-dideuterio-2-trideuterio-methylcyclopropanol 和(CD3)2CDH，通过质谱法鉴定。讨论了反应机理。

  DOI：

  10.1007/bf02494693

文献信息

• Studies on the origin of cis-diastereoselectivity of the titanium-mediated cyclopropanation of carboxylic esters with Grignard reagents. Stereochemistry of the intramolecular cyclization of β-metalloketones
  作者：Dzmitry G. Kananovich、Oleg G. Kulinkovich

  DOI：10.1016/j.tet.2007.10.075

  日期：2008.2

  Datа on the stereochemistry of the intramolecular cyclization of β-metaloketones into 1,2-disubstituted cyclopropanols are in agreement with the cyclopropanation of carboxylic esters with alkoxytitanacyclopropane reagents proceeding via the β-titanoketone intermediates with the metal atom bound to a secondary carbon. Hypothesis for the origin of cis-diastereoselectivity of the cyclization of the β-titanoketones

  关于将β-金属酮分子内环化为1,2-二取代的环丙醇的立体化学数据，与羧酸酯与烷氧基钛烷环丙烷试剂的环丙烷化反应是一致的，该反应是通过β-钛酮中间产物进行的，其中金属原子与仲碳相连。提出了关于β-钛酮环化的顺式-非对映选择性起源的假说。它解释了通过减轻八面体钛原子上的配体之间的排斥应变而优选形成顺式-1，2-二取代的环丙醇的趋势。
• B(C₆F₅)₃-Catalyzed transfer 1,4-hydrostannylation of α,β-unsaturated carbonyls using iPr-tricarbastannatrane
  作者：Eric Fillion、Azadeh Kavoosi、Kevin Nguyen、Christian Ieritano

  DOI：10.1039/c6cc07819b

  日期：——

  The hypercoordinated tin reagent iPr-tricarbastannatrane is employed in B(C₆F₅)₃-catalyzed transfer 1,4-hydrostannanylation of electron deficient olefins.

  超配位锡试剂iPr-tricarbastannatrane在B(C6F5)3催化的电子不足烯烃转移1,4-氢基锡化中被使用。
• Dulayymi, Juma'a R. Al; Baird, Mark S.; Bolesov, Ivan G., Journal of the Chemical Society. Perkin transactions II, 2000, # 7, p. 1603 - 1618
  作者：Dulayymi, Juma'a R. Al、Baird, Mark S.、Bolesov, Ivan G.、Nizovtsev, Alexey V.、Tverezovsky, Viacheslav V.

  DOI：——

  日期：——
• N-bromosuccinimide. Mechanisms of allylic bromination and related reactions
  作者：J. H. Incremona、James Cullen Martin

  DOI：10.1021/ja00706a034

  日期：1970.2
• Single and double hydrogen migration in the fragmentation of 3-methyl-2-butyl trifluoroacetate
  作者：Dan F??rcaşiu、Glen Miller、Chang S. Hsu

  DOI：10.1002/oms.1210250804

  日期：1990.8

  AbstractThree of the main oxygen‐containing fragments resulting from 3‐methyl‐2‐butyl trifluoroacetate (11) had been identified previously as the 1‐triflnoroacetoxyethyl cation (m/z 141, 12, product of simple cleavage), and the products of single (m/z 142) and double hydrogen transfer (m/z 143, protonated ethyl trifluoroacetate). Collisionally activated dissociation of m/z 142 and the isotopomers resulting from 11‐2‐d, 11‐1‐d3, 11‐5,6‐d6, and 11‐18O2 has established that m/z 142 is the oxygen protonated 1‐trifluoroacetoxyethyl free radical (17) formed by hydrogen shift irom a γ‐methyl group to oxygen in the molecular ion, rather than in a complex (18) between 12 and the 2‐propyl free radical, as expected based on a mechanistic model existing in the literature. The second hydrogen transferred originates in the other γ‐methyl group; its migration may occur, but does not have to, in the complex between 17 and a molecule of propene, prior to dissociation of the two fragments. Collision‐activated dissociation has now shown that the m/z 140 ion observed in the spectrum is the molecular ion of vinyl trifluoroacetate, possibly formed by a hydrogen transfer from 12 to the 2‐propyl radical in the complex 18. The hydrogen migration to oxygen exhibits no isotope effect, whereas the transfers to carbon atoms exhibit small primary and α secondary kinetic isotope effects. Exclusive migration of the tertiary hydrogen from C(3) occurs in the formation of 2‐methylbutene cation radical (m/z 70) from the molecular ion. The hydrocarbon ion fragments and the heteroatom‐containing fragments are formed from 11 by disjoint pathways.