(1S,2S)-2-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]-1-(methyldiphenylsilyl)cyclohexane | 935697-14-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (1S,2S)-2-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]-1-(methyldiphenylsilyl)cyclohexane
• 英文别名: Ph2MeSiC6H10C(CH2)Bpin；methyl-diphenyl-[(1S,2S)-2-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]cyclohexyl]silane
• CAS: 935697-14-6
• 化学式: C₂₇H₃₇BO₂Si
• 分子量: 432.486
• InChiKey: XJGUPCWPBQDWOB-DQEYMECFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.63
• 重原子数：
  31
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.48
• 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：

  (1S,2S)-2-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]-1-(methyldiphenylsilyl)cyclohexane 在 4-二甲氨基吡啶 、 sodium hydroxide 、 双氧水 、 N,N'-二环己基碳二亚胺 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 29.0h， 生成
  参考文献：
  名称：

  Palladium-Catalyzed Asymmetric Silaborative C−C Cleavage of meso-Methylenecyclopropanes

  摘要：

  An enantioselective silaborative C-C cleavage of meso-methylenecyclopropanes (meso-MCPs) was achieved by using a palladium catalyst bearing a chiral monodentate phosphine ligand. The (R)-2-bis(3,5-dimethylphenyl)phosphino-1,1'-binaphthyl gave the highest enantioselectivity in the reactions with (methyldiphenylsilyl)pinacolborane at 50 degrees C, affording derivatives of 2-boryl-4-silyl-1-butene in high yields with high enantiomeric excesses. The reactions of bicyclic MCPs that have fused five- to eight-membered rings gave the corresponding products with 89-91% ee, whereas a little lower ee was observed in the reaction of a non-fused MCP (81% ee). Synthetic applications of the products were demonstrated through synthesis of beta-silyl ketones by H2O2 oxidation and synthesis of stereodefined homoallylic alcohols via homologation-allylboration sequence, in which the chiral beta-substituent of the allylborane has critical impact on the diastereochemical outcome.

  DOI：

  10.1021/ja0703170
• 作为产物：
  描述：

  7-methylenebicyclo[4.1.0]heptane 、 2-(methyldiphenylsilyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 tris-(dibenzylideneacetone)dipalladium(0) 、 (1R,2r)-2-氨基-1,2-二苯乙醇 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以81%的产率得到(1S,2S)-2-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]-1-(methyldiphenylsilyl)cyclohexane
  参考文献：
  名称：

  手性放大，单手螺旋由手性客体动态诱导到带有硼基悬垂体作为受体位点的大分子手性催化剂

  摘要：

  通过与手性客体（例如二醇、二胺和氨基醇）缩合，在喹喔啉环的 5 位带有硼基侧链的聚（喹喔啉-2,3-二基）的螺旋手性被诱导。单手螺旋结构的可逆诱导是通过使用少于等摩尔量的手性氨基醇来实现的。使用具有低对映体过量 (ee) 的手性氨基醇证明了聚喹喔啉主链上基于多数规则效应的手性扩增。通过在侧链上引入（二芳基膦基）苯基侧链，由此诱导的螺旋大分子支架用于钯催化的内消旋亚甲基环丙烷（高达 92% ee）的不对称硅化反应。

  DOI：

  10.1021/jacs.8b00529

文献信息

• Enhanced Catalyst Activity and Enantioselectivity with Chirality-Switchable Polymer Ligand PQXphos in Pd-Catalyzed Asymmetric Silaborative Cleavage of <i>meso</i>-Methylenecyclopropanes
  作者：Yuto Akai、Takeshi Yamamoto、Yuuya Nagata、Toshimichi Ohmura、Michinori Suginome

  DOI：10.1021/ja303506k

  日期：2012.7.11

  The poly(quinoxaline-2,3-diyl)-based helically chiral phosphine ligands PQXphos exhibited high enantioselectivities up to 97% ee in palladium-catalyzed desymmetrization of meso-1,2-dialkylsubstituted-3-methylenecyclopropanes through silaborative cleavage of the C C bond. The observed enantioselectivities were higher than those obtained with 2-diarylphosphino-1,1'-binaphthyl in our original report. Remarkable rate enhancement was also observed with a series of PQXphos in comparison with the corresponding low-molecular weight ligands.
• Kinetic Resolution of Racemic 1-Alkyl-2-methylenecyclopropanes via Palladium-Catalyzed Silaborative C−C Cleavage
  作者：Toshimichi Ohmura、Hiroki Taniguchi、Michinori Suginome

  DOI：10.1021/ol900829c

  日期：2009.7.2

  Kinetic resolution of racemic 1-alkyl-2-methylenecyclopropanes via silaborative C-C cleavage was efficiently catalyzed by a palladium complex bearing a chiral phosphoramidite, affording 2-boryl-3-silylmethyl-1-alkenes as major products with up to 92% ee. Enantioenrichment through parallel kinetic resolution, where the slower reacting enantiomer was converted to the constitutional isomer of the major product, may be involved as the crucial stereodiscriminating step.