1,3-dimethyl-1,3,2λ²-diazaborolidine,trimethyltin | 36333-59-2

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 1,3-dimethyl-1,3,2λ²-diazaborolidine,trimethyltin
• 英文别名: 1,3-dimethyl-2-(trimethylstannyl)-2-bora-1,3-diazacyclopentane；1,3-dimethyl-2-trimethylstannyl-2-bora-1,3-diazacyclopentane；1,3-dimethyl-2-trimethylstannyl-1,3,2-diazaborolane
• CAS: 36333-59-2
• 化学式: C₇H₁₉BN₂Sn
• 分子量: 260.762
• InChiKey: XETHPYUFEOVIMG-UHFFFAOYSA-N

物化性质

• 沸点：
  66-69 °C(Press: 4 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  0.77
• 重原子数：
  11.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  6.48
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1,3-dimethyl-1,3,2λ²-diazaborolidine,trimethyltin 、 2,2'-bis(prop-2-ynyl)-1,1'-biphenyl 在 Pd₂(OC(CHCHC₆H₅)2)3*CHCl₃ 、 (C₁₀H₆O)2PN(CH(CH₃)C₆H₅)2 作用下， 以 not given 为溶剂， 以75%的产率得到
  参考文献：
  名称：

  Stereoselective Cyclization of Functionalized 1,n-Diynes Mediated by [X−Y] Reagents [X−Y = R₃Si−SnR′₃ or (R₂N)₂B−SnR′₃]: Synthesis and Properties of Atropisomeric 1,3-Dienes

  摘要：

  The borylstannane [-N(Me)CH2CH2(Me)N-]B-SnMe3 is a superior reagent capable of effecting bisfunctionalization-cyclization in several highly functionalized 1,n-diynes, 1,n-enynes, and 1,n-allenynes (including 1,2-dipropargylbenzenes, 2,2'-dipropargylbiphenyls, 4,5-dipropargyldioxolanes, and 1,4-dipropargyl-beta -lactams) where the more well-known silylstannanes fail. Variable-temperature NMR studies showed that conformational restraints imposed by selected backbones increase the activation barrier for the helical isomerization in (Z,2)-dienes that are generated in the cyclization of the diynes. In the biphenyl and dioxolane systems, the reactions proceed with surprisingly good regio- and stereoselectivity. The resulting diazaborolidine derivatives are hydrolytically unstable but can be isolated by recrystallization or precipitation. For further synthetic applications, it is advantageous to convert these compounds in situ into the corresponding dioxaborolidines with either retention of the Me3Sn group or replacement of this group via halodestannylation. The configurations of the vinyl moieties are preserved in these reactions. Highly functionalized dibenzocyclooctadienes, which adorn the carbon frames of several important cytotoxic natural products, can be synthesized using this chemistry.

  DOI：

  10.1021/ja105939v
• 作为试剂：
  描述：

  diethyl 2,3-butadien-1-yl-propargyl-malonate 、 频哪醇 在 1,3-dimethyl-1,3,2λ²-diazaborolidine,trimethyltin 、 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 三(五氟苯基)膦 、 对甲苯磺酸 作用下， 以 氯仿 、 苯 为溶剂， 反应 6.5h， 生成
  参考文献：
  名称：

  Stereoselective Cyclization of Functionalized 1,n-Diynes Mediated by [X−Y] Reagents [X−Y = R₃Si−SnR′₃ or (R₂N)₂B−SnR′₃]: Synthesis and Properties of Atropisomeric 1,3-Dienes

  摘要：

  The borylstannane [-N(Me)CH2CH2(Me)N-]B-SnMe3 is a superior reagent capable of effecting bisfunctionalization-cyclization in several highly functionalized 1,n-diynes, 1,n-enynes, and 1,n-allenynes (including 1,2-dipropargylbenzenes, 2,2'-dipropargylbiphenyls, 4,5-dipropargyldioxolanes, and 1,4-dipropargyl-beta -lactams) where the more well-known silylstannanes fail. Variable-temperature NMR studies showed that conformational restraints imposed by selected backbones increase the activation barrier for the helical isomerization in (Z,2)-dienes that are generated in the cyclization of the diynes. In the biphenyl and dioxolane systems, the reactions proceed with surprisingly good regio- and stereoselectivity. The resulting diazaborolidine derivatives are hydrolytically unstable but can be isolated by recrystallization or precipitation. For further synthetic applications, it is advantageous to convert these compounds in situ into the corresponding dioxaborolidines with either retention of the Me3Sn group or replacement of this group via halodestannylation. The configurations of the vinyl moieties are preserved in these reactions. Highly functionalized dibenzocyclooctadienes, which adorn the carbon frames of several important cytotoxic natural products, can be synthesized using this chemistry.

  DOI：

  10.1021/ja105939v

文献信息

• Palladium-catalysed borylsilylation and borylstannylative dimerization of 1,2-dienes
  作者：Shun-ya Onozawa、Yasuo Hatanaka、Masato Tanaka

  DOI：10.1039/a905127i

  日期：——

  A borylsilane regioselectively adds to 1,2-dienes in the presence of palladium complexes to afford high yields of alkenylboranes having allylsilane moieties, whereas a borylstannane gives a 1 : 2 telomer with 3-methylbuta-1,2-diene due to borylstannylative dimerization.

  在钯配合物的存在下，硼硅烷选择性地与1,2-二烯加成，得到含有烯丙基硅烷片段的高产率烯基硼烷，而硼锡烷则通过硼锡烷化二聚反应与3-甲基丁-1,2-二烯形成1:2的调聚物。
• Palladium-Catalyzed Borylstannylative Carbocyclization of Diynes and an Enyne Compound
  作者：Shun-ya Onozawa、Yasuo Hatanaka、Nami Choi、Masato Tanaka

  DOI：10.1021/om970704q

  日期：1997.12.1

  Highly regio- and stereoselective borylstannylative carbocyclization of diynes 2a−f with the borylstannane 1 are efficiently catalyzed at room temperature by a series of palladium complexes such as Cl2Pd(PPh3)2, Cl2Pd[P(o-tolyl)3]2, Pd(PPh3)4, and Pd(dba)2, giving 1-(borylmethylidene)-2-(stannylmethylidene)cycloalkane derivatives 3a−f in high yields. A 1,6-enyne (2g) also reacts similarly to afford

  二炔的高度区域选择性和立体选择性borylstannylative carbocyclization 2A - ˚F与borylstannane 1被有效地由一系列钯络合物如Cl在室温下催化2的Pd（PPh 3）2，氯2的Pd [P（邻甲苯基）3 ] 2，Pd（PPh 3）4和Pd（dba）2，以高收率得到1-（硼烷基亚甲基）-2-（锡烷基亚甲基）环烷烃衍生物3a - f。1，6-烯炔（2g）的反应也相似，可提供高产率的相应环化产物3克。
• Conformation and reactivity in dibenzocyclooctadienes (DBCOD). A general approach to the total synthesis of fully substituted DBCOD lignans via borostannylative cyclization of α,ω-diynes
  作者：Wei Gong、T. V. RajanBabu

  DOI：10.1039/c3sc51751a

  日期：——

  Pd(II)-catalysts, to give highly functionalized DBCOD precursors. The configuration of the newly created, axially chiral, 1,2-bis-alkylidene moiety is controlled by the resident chirality of the starting biphenyls and the configurations of the benzylic positions. New chemistry of the bis-alkylidenes described in this paper enables the first total syntheses of a wide variety of DBCOD natural products, fully functionalized

  二苯并环辛二烯（DBCOD）是一类植物来源的天然产物，具有广泛的生物活性。这些包括细胞毒性，抗乙型肝炎活性，抑制HIV复制以及NO的产生和活性。之前尚未准备完全取代的DBCOD。2,2'-二炔丙基联苯经历由[B-Sn]试剂1-三甲基锡烷基-2,5-二氮杂硼烷（Me 3 Sn–B [–N（Me）CH 2 CH 2（ Me）N–]，在Pd（II）催化剂，得到高度官能化的DBCOD前体。新产生的轴向手性1,2-双亚烷基部分的构型由起始联苯的固有手性和苄基位置的构型控制。本文所述的双亚烷基的新化学方法能够首次全面合成在环辛二烯环上完全官能化的多种DBCOD天然产物。其中包括Ananolignans B，C，D，F，interotherotherin C，kadsuralignan B，tiegusanin D和schizanrinF。还报道了对关键天然产物Ananolignan B的结构的修订。合
• The Chemistry of Borylstannanes:  Oxidative Addition to Palladium Species and Its Application to Palladium-Catalyzed Borylstannation of Alkynes
  作者：Shun-ya Onozawa、Yasuo Hatanaka、Toshiyasu Sakakura、Shigeru Shimada、Masato Tanaka

  DOI：10.1021/om9607199

  日期：1996.12.24

  cis addition of the borylstannanes Me(3)SnB[NMe(CH2CH2)NMe] (1) and Me(3)SnB(NEt(2))(2) (4) across alkynes was efficiently catalyzed at room temperature or 80 degrees C by Pd(PPh(3))(4), Pd(dba)(2), Cl2Pd(PPh(3))(2), or Me(2)Pd[PMe(2)(CH2CH2)PMe(2)] to give (beta-stannylalkenyl)boranes in high yields. Treatments of 1 with Me(2)Pd[PMe(2)(CH2CH2)PMe(2)] and of 4 with cis-Me(2)Pd(PPh(2)Me)(2) gave [MeN(CH2CH2)Men}B](Me(3)Sn)Pd[PMe(2) (CH2CH2)-PMe(2)] (5) and [(Et(2)N)(2)B](Me(3)Sn)Pd(PPh(2)Me)(2) (6), respectively, with the former characterized by X-ray analysis. Complex 5, when treated with 1-octyne, formed the corresponding (beta-stannyl-1-octen-1-yl)borane and could catalyze the addition reaction of 1 with 1-octyne.