azidobis(trimethylsilyl)methane | 134340-01-5

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: azidobis(trimethylsilyl)methane
• 英文别名: bis(trimethylsilyl)methyl azide；1,1a(2)-(Azidomethylene)bis[1,1,1-trimethylsilane]；[azido(trimethylsilyl)methyl]-trimethylsilane
• CAS: 134340-01-5
• 化学式: C₇H₁₉N₃Si₂
• 分子量: 201.419
• InChiKey: LFXTXZCHNJRTCE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.42
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  14.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  azidobis(trimethylsilyl)methane 以 四氢呋喃 、 甲苯 为溶剂， 反应 6.0h， 生成 Bis(trimethylsilyl)methyl isothiocyanate
  参考文献：
  名称：

  Synthesis and Reactivity of N-[Bis(trimethylsilyl)methyl]heterocumulenes

  摘要：

  A number of N-heterocumulenes bearing the (Me(3)Si)(2)CH (BSM) substituent adjacent to the terminal nitrogen atom of the heterocumulene function, namely BSM-N=C=O (2), BSM-N=C=S (3), BSM-N=C=NR(4: R = BSM; 5: R = C6H5), BSM-N=C=CR(1)R(2) (9a: R(1) = R(2) = C6H5; 9b: R(1) = H, R(2) = SiMe(3); 10: R(1) = R(2) = CH3; 12: R(1) = H; R(2) = CH3), and BSM-N=S=O (14), have been synthesized. The synthetic utility of the BSM-N-substituted heterocumulenes has been explored through the creation of a carbanion center at the a position relative to nitrogen. In particular, the following reactions have been studied: (i) the nucleophilic addition of MeLi to compounds 2 and 5, (ii) the MeLi-induced deprotonation of ketene imines 9a,b (this investigation includes the study of the regiochemical output of the addition of electrophiles (H2O, Mel, Me(2)CHI) to the resulting 1,3-dipoles; and (iii) the TBAF-induced desilylation of compounds 2 and 9a followed by reaction with benzaldehyde.

  DOI：

  10.1021/jo00124a011
• 作为产物：
  描述：

  二(三甲基硅基)氯甲烷 在 六甲基磷酰三胺 、 sodium azide 作用下， 反应 5.0h， 生成 azidobis(trimethylsilyl)methane
  参考文献：
  名称：

  A novel highly stereoselective synthesis of pyrrolidines and their derivatives through thermal cyclization reaction of N-[bis(trimethylsilyl)methyl]-1-aza-1,3-dienes

  摘要：

  报道了 N-[双(三甲基甲硅烷基)甲基]-1-氮杂-1,3-二烯热分子内环化生成 5-三甲基甲硅烷基-Δ2-吡咯啉的第一个例子；还描述了两种直接且高度立体选择性的3,4-二取代-5-三甲基甲硅烷基-Δ1吡咯啉和3,4-二取代-2-三甲基甲硅烷基吡咯烷路线。

  DOI：

  10.1039/c39910000524

文献信息

• Cationic 1,2,3-Triazolium Alkynes: Components To Enhance 1,4-Regioselective Azide–Alkyne Cycloaddition Reactions
  作者：Zaira Monasterio、Maialen Sagartzazu-Aizpurua、José I. Miranda、Yuri Reyes、Jesus M. Aizpurua

  DOI：10.1021/acs.orglett.6b00055

  日期：2016.2.19

  thermal [3 + 2] cycloaddition reactions with azides roughly 50- to 100-fold faster than comparable noncharged alkynes. Further, the reaction is highly 1,4-regioselective (dr up to 99:1) owing to the selective stabilization of 1,4-TS transition states via conjugative π-acceptor assistance of the alkyne triazolium ring. The novel cationic triazolium alkynes also accelerate the CuAAC reaction to provide bis(1

  4-炔基-1,2,3-三唑鎓阳离子经历热[3 + 2]环加成反应，叠氮化物的速度比不带电的炔烃快50到100倍。此外，由于经由炔三唑环的共轭π-受体辅助的1,4-TS过渡态的选择性稳定，该反应是高度1,4-区域选择性的（dr高达99：1）。新型阳离子三唑鎓炔烃还可以加速CuAAC反应，以“超快”方式（<5分钟）提供双（1,2,3-三唑）。
• A novel highly stereoselective synthesis of pyrrolidines and their derivatives through thermal cyclization reaction of N-[bis(trimethylsilyl)methyl]-1-aza-1,3-dienes
  作者：Claudio Palomo、Jesus M. Aizpurua、Jesus M. García、Marta Legido

  DOI：10.1039/c39910000524

  日期：——

  The first example of the thermal intramolecular cyclization of N-[bis(trimethylsilyl)methyl]-1-aza-1,3-dienes to give 5-trimethylsilyl-Δ2-pyrrolines is reported; two straightforward and highly Stereoselective routes to 3,4-disubstituted-5-trimethylsilyl-Δ1pyrrolines and 3,4-disubstituted-2-trimethylsilylpyrrolidines are also described.

  报道了 N-[双(三甲基甲硅烷基)甲基]-1-氮杂-1,3-二烯热分子内环化生成 5-三甲基甲硅烷基-Δ2-吡咯啉的第一个例子；还描述了两种直接且高度立体选择性的3,4-二取代-5-三甲基甲硅烷基-Δ1吡咯啉和3,4-二取代-2-三甲基甲硅烷基吡咯烷路线。
• Synthesis and Reactivity of N-[Bis(trimethylsilyl)methyl]heterocumulenes
  作者：Gaetano Barbaro、Arturo Battaglia、Patrizia Giorgianni、Andrea Guerrini、Giancarlo Seconi

  DOI：10.1021/jo00124a011

  日期：1995.9

  A number of N-heterocumulenes bearing the (Me(3)Si)(2)CH (BSM) substituent adjacent to the terminal nitrogen atom of the heterocumulene function, namely BSM-N=C=O (2), BSM-N=C=S (3), BSM-N=C=NR(4: R = BSM; 5: R = C6H5), BSM-N=C=CR(1)R(2) (9a: R(1) = R(2) = C6H5; 9b: R(1) = H, R(2) = SiMe(3); 10: R(1) = R(2) = CH3; 12: R(1) = H; R(2) = CH3), and BSM-N=S=O (14), have been synthesized. The synthetic utility of the BSM-N-substituted heterocumulenes has been explored through the creation of a carbanion center at the a position relative to nitrogen. In particular, the following reactions have been studied: (i) the nucleophilic addition of MeLi to compounds 2 and 5, (ii) the MeLi-induced deprotonation of ketene imines 9a,b (this investigation includes the study of the regiochemical output of the addition of electrophiles (H2O, Mel, Me(2)CHI) to the resulting 1,3-dipoles; and (iii) the TBAF-induced desilylation of compounds 2 and 9a followed by reaction with benzaldehyde.
• Fluoride ion mediated peterson alkenation of N-[C,C-bis(trimethylsilyl)methyl]amido derivatives with carbonyl compounds: a short general route to enamides and 1,2-dihydroisoquinolines.
  作者：Claudio Palomo、Jesús M. Aizpurua、Marta Legido、Jean Paul Picard、Jacques Dunogues、Thierry Constantieux

  DOI：10.1016/s0040-4039(00)74815-5

  日期：1992.6

  A straightforward general access to diversely substituted acyclic or cyclic enamides and dienamides is accomplished by using a fluoride induced Peterson olefination of carbonyl compounds and enolizable amides derived from C,C-bis(trimethylsilyl) methylamine.