(+/-)-B-[(Z)-γ-methoxyallyl]-10-trimethylsilyl-9-borabicyclo[3.3.2]decane | 1161746-12-8

• 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: (+/-)-B-[(Z)-γ-methoxyallyl]-10-trimethylsilyl-9-borabicyclo[3.3.2]decane
• 英文别名: (+/-)-B-[(Z)-(γ-methoxyallyl)]-10-TMS-9-BBD；[9-[(Z)-3-methoxyprop-2-enyl]-9-borabicyclo[3.3.2]decan-10-yl]-trimethylsilane
• CAS: 1161746-12-8
• 化学式: C₁₆H₃₁BOSi
• 分子量: 278.318
• InChiKey: JKIBMOPKPPSEEP-QPEQYQDCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.24
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-B-[(Z)-γ-methoxyallyl]-10-trimethylsilyl-9-borabicyclo[3.3.2]decane 以 正戊烷 为溶剂， 反应 96.0h， 生成 (+/-)-B-[(E)-γ-methoxyallyl]-10-trimethylsilyl-9-borabicyclo[3.3.2]decane
  参考文献：
  名称：

  Asymmetric γ-Methoxyallylation with the Robust 10-TMS-9-Borabicyclo[3.3.2]decanes

  摘要：

  The asymmetric gamma-methoxyallylboration of aldehydes with the configurationally very stable 1 gives nonracemic threo-beta-methoxyhomoallylic alcohols 7 (65-93%) with excellent selectivity (96-99% de, 98-99% ee). The corresponding homoallylic amines 10 are obtained from N-H aldimines with similar efficiency (72-96%) and with excellent diastereoselectivity (98% de) but with lower enantioselectivity (56-86% ee). These new reagents provide ready access to a Taxol side chain derivative.

  DOI：

  10.1021/ol900865y
• 作为产物：
  描述：

  B-甲氧基-10-三甲基甲硅烷基-9-硼二环(3.3.2)癸烷 、 烯丙基甲基醚 在 仲丁基锂 、 三甲基氯硅烷 作用下， 以 四氢呋喃 、 环己烷 为溶剂， 反应 2.5h， 生成 (+/-)-B-[(Z)-γ-methoxyallyl]-10-trimethylsilyl-9-borabicyclo[3.3.2]decane
  参考文献：
  名称：

  Asymmetric γ-Methoxyallylation with the Robust 10-TMS-9-Borabicyclo[3.3.2]decanes

  摘要：

  The asymmetric gamma-methoxyallylboration of aldehydes with the configurationally very stable 1 gives nonracemic threo-beta-methoxyhomoallylic alcohols 7 (65-93%) with excellent selectivity (96-99% de, 98-99% ee). The corresponding homoallylic amines 10 are obtained from N-H aldimines with similar efficiency (72-96%) and with excellent diastereoselectivity (98% de) but with lower enantioselectivity (56-86% ee). These new reagents provide ready access to a Taxol side chain derivative.

  DOI：

  10.1021/ol900865y

文献信息

• Highly Functionalized <i>tertiary-</i>Carbinols and Carbinamines from the Asymmetric γ-Alkoxyallylboration of Ketones and Ketimines with the Borabicyclodecanes
  作者：Lorell Muñoz-Hernández、Luis A. Seda、Bo Wang、John A. Soderquist

  DOI：10.1021/ol5019486

  日期：2014.8.1

  asymmetric γ-alkoxyallylboration of representative ketones provides β-alkoxy tert-homoallylic alcohols 10 whose diastereoselectivities range from 99% syn (acetophenone) to 99% anti (pinacolone) both with high ee (>95%). This distribution is attributable to the c/t isomerization of the BBD reagents and the greater reactivity of 7 vs 1 and of aromatic vs alkyl ketones. A ketone-based direct synthesis of a fostriecin

  代表性酮的第一个不对称的γ-烷氧基烯丙基化提供了β-烷氧基叔-烯丙基醇10，其非对映选择性范围从99％的顺式（苯乙酮）到99％的反式（频哪酮）具有较高的ee（> 95％）。该分布归因于BBD试剂的c / t异构化以及7对1和芳族对烷基酮的更高反应性。一个fostriecin中间的酮系直接合成和叔-胺26被报告，每个具有高的选择性。
• Asymmetric γ-Methoxyallylation with the Robust 10-TMS-9-Borabicyclo[3.3.2]decanes
  作者：Lorell Muñoz-Hernández、John A. Soderquist

  DOI：10.1021/ol900865y

  日期：2009.6.18

  The asymmetric gamma-methoxyallylboration of aldehydes with the configurationally very stable 1 gives nonracemic threo-beta-methoxyhomoallylic alcohols 7 (65-93%) with excellent selectivity (96-99% de, 98-99% ee). The corresponding homoallylic amines 10 are obtained from N-H aldimines with similar efficiency (72-96%) and with excellent diastereoselectivity (98% de) but with lower enantioselectivity (56-86% ee). These new reagents provide ready access to a Taxol side chain derivative.