(-)-B-甲氧基二异松莰基硼烷 | 85134-98-1

• 物质功能分类: 化学试剂 - 有机试剂 - 硼烷
• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 中文名称: (-)-B-甲氧基二异松莰基硼烷
• 中文别名: (+)-B-甲氧基二异松莰基硼烷；(-)-B-甲氧基二异松蒎基硼烷；(-)-二异松蒎基甲氧基硼烷
• 英文名称: (-)-B-methoxy-diisopinocamphenylborane
• 英文别名: (+)-B-methoxydiisopinocamphenylborane；(+)-B-methoxydiisopinocampheylborane；B-methoxydiisopinocampheylborane；methoxydiisopinocampheylborane；(-)-B-methoxydiisopinocampheyl borane；(-)-B-methoxydiisopinocampheylborane；methoxy-bis(2,6,6-trimethyl-3-bicyclo[3.1.1]heptanyl)borane
• CAS: 85134-98-1；99438-28-5
• 化学式: C₂₁H₃₇BO
• 分子量: 316.335
• InChiKey: IAQXEQYLQNNXJC-UHFFFAOYSA-N

物化性质

• 沸点：
  365.6±9.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)
• 闪点：
  >230 °F

计算性质

• 辛醇/水分配系数(LogP)：
  5.77
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 危险品标志：
  Xi
• 安全说明：
  S26,S36
• 危险类别码：
  R36/37/38
• WGK Germany：
  3
• 海关编码：
  2931900090

制备方法与用途

用途：（+）-和（-）-形式均为B-烯丙基二异松蒎基硼烷衍生物的前体。这两种形式随后与醛反应，生成具有高光学纯度的高烯丙醇和β-氨基酸。

反应信息

• 作为反应物：
  描述：

  3-((2-methoxyethoxy)methoxy)prop-1-ene 、 (-)-B-甲氧基二异松莰基硼烷 在 仲丁基锂 作用下， 以 四氢呋喃 、 环己烷 为溶剂， 反应 1.5h， 生成 (+)-B-γ-methoxyethoxymethoxyallyldiisopinocamphenylborane
  参考文献：
  名称：

  通过CSI介导的立体选择性胺化反应合成3-羟基哌酸类似物并进行构象分析

  摘要：

  一种短而有效的立体选择性合成方法，涉及取代的哌啶，涉及（2 S，3 S）-3-羟基哌酸1，（2 R，3 S）-3-羟基哌酸3，以及它们的酸还原类似物2和4，已经被开发出来。必要的抗-和顺-1,2-氨基醇11和12用于制备标题四个哌啶类似物1 - 4分别通过的区域选择性和对映选择性合成胺化抗和-顺使用氯磺酰基异氰酸酯（CSI）的-1,2-二苄基醚13和14。其结果是，反应的反-1,2-二苄基醚13与CSI只得到反-1,2-氨基醇11与49的非对映选择性：1在甲苯中在-78℃和顺式-异构体14，得到以-1,2-氨基醇12为主要产物，在-78°C下在己烷中的非对映异构体选择性为12：1。这些反应的结果可以由导致立体化学保留的邻近基团效应来解释。另外，反式的构象变化就N-保护基的性质描述了-哌啶中间体9。1 H NMR分析和NOE相关性证实了9和24 – 28的构象。此外，通过NMR光谱研究了在C

  DOI：

  10.1016/j.tet.2007.01.028
• 作为产物：
  描述：

  甲醇 、 Pinene 在 tert-butylbis(2-methoxyethyl)amine-borane 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 生成 (-)-B-甲氧基二异松莰基硼烷 、 Dimethoxy-(2,6,6-trimethyl-3-bicyclo[3.1.1]heptanyl)borane
  参考文献：
  名称：

  Molecular Addition Compounds. 15. Synthesis, Hydroboration, and Reduction Studies of New, Highly Reactive tert-Butyldialkylamine−Borane Adducts

  摘要：

  Two series of tert-butyldialkylamines have been prepared and examined for borane complexation. The complexing ability of each amine in the two series examined decreases in the order shown. First series: t-BuN(CH2CH2)(2)O 1a > t-BuNEt2 Ib > t-BuNPr(2)(n)1c > t-BuN(CH2CH2OMe)(2) Id much greater than t-BuNBu2i le. Second series: t-(BuNBuMe)-Me-i 2a > t-(BuNPrMe)-Me-i 2b > t-(BuNBuEt)-Et-i 2c > t-(BuNBuPrn)-Pr-i 2d much greater than t-(BuNPrEt)-Et-i 2e. The reactivity of the corresponding borane adducts toward 1-octene increases in the reverse order. The following amines form highly reactive liquid borane adducts hydroborating 1-octene in tetrahydrofuran at room temperature in less than 1 h: t-BuN(CH2CH2OMe)(2), t-(BuNBuEt)-Et-i, and t-(BuNPrMe)-Me-i. The limit of borane complexation among the amines examined is reached for t-BuNBu2i exchanging borane neither with EMS nor with BH3-THF. Among the various borane adducts prepared, the more promising borane adducts, t-Bu(CH3OCH2CH2)(2)N-BH3 (7), t-(BuMePrN)-N-i-BH3 (8), and t-(BuEtBuN)-N-i-BH3 (9), were selected for complete hydroboration and reduction studies. Hydroboration studies with the new, highly reactive trialkylamine-borane adducts 7-9 and representative olefins, such as l-hexene, styrene, beta-pinene, cyclopentene, norbornene, cyclohexene, 2-methyl-2-butene, alpha-pinene, and 2,3-dimethyl-2-butene, in tetrahydrofuran, dioxane, tert-butyl methyl ether, n-pentane, and dichloromethane, at room temperature (22 +/- 3 degrees C) were carried out. The reactions are faster in dioxane, requiring 1-2 h for the hydroboration of simple, unhindered olefins to the trialkylborane stage. Moderately hindered olefins, such as cyclohexene and 2-methyl-2-butene, give the corresponding dialkylboranes rapidly, with further slow hydroboration. However, the more hindered olefins, alpha-pinene and 2,3-dimethyl-2-butene, give stable monoalkylboranes very rapidly, with further hydroboration proceeding relatively slowly. The hydroborations can also be carried out conveniently in other solvents, such as THF, tert-butyl methyl ether, and n-pentane. A significant; rate retardation is observed in dichloromethane. Regioselectivity studies of l-hexene and styrene using these amine-borane adducts show selectivities similar to that of BH3-THF. The rates and stoichiometry of the reaction of t-BuMePriN-BH3 in tetrahydrofuran with selected organic compounds containing representative functional groups were also examined at room temperature. The reductions of esters, amides, and nitriles, which exhibit a sluggish reaction at room temperature, proceed readily under reflux conditions in tetrahydrofuran and dioxane and without solvent (at 85-90 degrees C). The carrier amines can be recovered by simple acid-base manipulations in good yield and readily recycled to make the borane adducts.

  DOI：

  10.1021/jo990379b
• 作为试剂：
  描述：

  3-(tert-butyldiphenylsilyloxy)-1-propanal 在 2,6-二甲基吡啶 、 titanium(IV) isopropylate 、 正丁基锂 、 四甲基乙二胺 、 三氟化硼乙醚 、 potassium tert-butylate 、 臭氧 、 (-)-B-甲氧基二异松莰基硼烷 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 10.5h， 生成 <3R,4S,5R,6R<2S-(2-tetrahydropyranyl)oxy>>-1-<<(tert-butyldiphenyl)silyl>oxy>-8-<(N,N-diisopropyl)carbamate>-5-hydroxy-4-methyl-6-<2-<(2-tetrahydropyranyl)oxy>ethyl>-3-<<(triisopropyl)silyl>oxy>oct-7-ene
  参考文献：
  名称：

  Allyltitanates in Stereospecific Additions to Chiral δ-Lactol:  Efficient Enantioselective Route to a Potential Precursor of the C1−C9 Portion of Tylonolide

  摘要：

  The Hoppe reaction, which is an allylation reaction of aldehydes using an optically active titanated crotyl carbamate intermediate generated from the corresponding N,N-diisopropyl crotyl carbamate with n-BuLi/(-)-sparteine, was in most cases applied to achiral aldehydes. In this work an extension of this reaction is reported using a racemic gamma-alkoxy allyltitanate (17) and an optically active aldehyde (16) to deliver in good yield the anti adduct 18 as the major isomer. When the corresponding delta-lactol 24 was used in place of aldehyde 16, the anti adduct 25 was obtained in 94% yield as the only product. Structural modifications effected on 25 delivered aldehyde 28 which was in turn submitted to a second allylation reaction in the presence of the optically active titanated crotyl carbamate 2, prepared as described by Hoppe from crotyl carbamate 1, to conduct to compound 29 in 80% yield. This derivative corresponds to a potential precursor of the C1-C9 portion of Tylonolide, aglycon of Tylosin (4).

  DOI：

  10.1021/jo9807722

文献信息

• Total Synthesis of Marinomycins A−C and of Their Monomeric Counterparts Monomarinomycin A and <i>iso</i>-Monomarinomycin A
  作者：K. C. Nicolaou、Andrea L. Nold、Robert R. Milburn、Corinna S. Schindler、Kevin P. Cole、Junichiro Yamaguchi

  DOI：10.1021/ja068053p

  日期：2007.2.1

  Marinomycins A-C (1-3), and their monomeric analogues monomarinomycin A (m-1) and iso-monomarinomycin A (m-2), were synthesized by a convergent strategy from key building blocks ketophosphonate 5, aldehyde 6, and dienyl bromide carboxylic acid 7. The first attempt to construct marinomycin A [1, convertible to marinomycins B (2) and C (3) by light] by direct Suzuki-type dimerization/cyclization of boronic

  Marinomycins AC (1-3) 及其单体类似物 monomarinomycin A (m-1) 和 iso-monomarinomycin A (m-2)，是通过聚合策略从关键结构单元酮膦酸酯 5、醛 6 和二烯溴化羧基合成的酸 7. 首次尝试通过硼酸二烯基溴 4 的直接铃木型二聚/环化来构建海藻霉素 A [1，可通过光转化为海藻霉素 B (2) 和 C (3)]，导致过早闭环，在全局脱甲硅烷基化后，monomarinomycin A (m-1) 和 iso-monomarinomycin A (m-2) 收率良好，并且只有少量 (< 或 = 2%) 的所需产物。随后基于 Suzuki 型偶联的逐步方法显着提高了海藻霉素 A (1) 的总产率，从而显着提高了海藻霉素 B (2) 和 C (3) 的总产率。
• Synthesis and conformational analysis of 3-hydroxypipecolic acid analogs via CSI-mediated stereoselective amination
  作者：In Su Kim、Joa Sub Oh、Ok Pyo Zee、Young Hoon Jung

  DOI：10.1016/j.tet.2007.01.028

  日期：2007.3

  the neighboring group effect leading to retention of stereochemistry. In addition, conformational changes of trans-piperidine intermediate 9 in terms of the nature of N-protecting groups are described. The conformations of 9 and 24–28 were confirmed by 1H NMR analysis and NOE correlation. Furthermore, the conformations of piperidines 18 and 23 with hydroxyl methyl substituent at C-2 were investigated

  一种短而有效的立体选择性合成方法，涉及取代的哌啶，涉及（2 S，3 S）-3-羟基哌酸1，（2 R，3 S）-3-羟基哌酸3，以及它们的酸还原类似物2和4，已经被开发出来。必要的抗-和顺-1,2-氨基醇11和12用于制备标题四个哌啶类似物1 - 4分别通过的区域选择性和对映选择性合成胺化抗和-顺使用氯磺酰基异氰酸酯（CSI）的-1,2-二苄基醚13和14。其结果是，反应的反-1,2-二苄基醚13与CSI只得到反-1,2-氨基醇11与49的非对映选择性：1在甲苯中在-78℃和顺式-异构体14，得到以-1,2-氨基醇12为主要产物，在-78°C下在己烷中的非对映异构体选择性为12：1。这些反应的结果可以由导致立体化学保留的邻近基团效应来解释。另外，反式的构象变化就N-保护基的性质描述了-哌啶中间体9。1 H NMR分析和NOE相关性证实了9和24 – 28的构象。此外，通过NMR光谱研究了在C
• Enantiomeric Z- and E-crotyldiisopinocampheylboranes. Synthesis in high optical purity of all four possible stereoisomers of .beta.-methylhomoallyl alcohols
  作者：Herbert C. Brown、Krishna S. Bhat

  DOI：10.1021/ja00262a017

  日期：1986.1

  Synthese des 4 stereoisomeres du methyl-3 pentene-4 ol-2 par reaction de (butene-2 diisopinocamphenyl) borane avec l'acetaldehyde

  Synthese des 4stereoisomeres dumethyl-3 pentene-4 ol-2 par 反应 de (butene-2 diisopinocamphenyl) borane avec l'acetaldehyde
• Synthetic spiroketal pyranes as potent anti-cancer agents and use
  申请人：Parker Hughes Institute

  公开号：US06512003B2

  公开（公告）日：2003-01-28

  Novel tubulin binding compounds (SPIKETS) having potent tubulin depolymerization activity and inhibitory activity against tubulin polymerization. The compounds are effective agents for inhibiting cellular proliferation, for example, in cancer cells. The compounds are adapted to interact favorably with a novel SP binding pocket on tubulin, which pocket is useful for screening of anti-tubulin, anti-proliferation, and anti-cancer drugs.

  新型微管蛋白结合化合物（SPIKETS）具有强大的微管蛋白去聚合作用和抑制微管蛋白聚合作用的活性。这些化合物是有效的细胞增殖抑制剂，例如在癌细胞中。这些化合物适应于与微管蛋白上的新型SP结合口袋有利地相互作用，该口袋对筛选抗微管蛋白、抗增殖和抗癌药物非常有用。
• Molecular Addition Compounds. 15. Synthesis, Hydroboration, and Reduction Studies of New, Highly Reactive <i>tert</i>-Butyldialkylamine−Borane Adducts
  作者：Herbert C. Brown、Josyula V. B. Kanth、Pramod V. Dalvi、Marek Zaidlewicz

  DOI：10.1021/jo990379b

  日期：1999.8.1

  Two series of tert-butyldialkylamines have been prepared and examined for borane complexation. The complexing ability of each amine in the two series examined decreases in the order shown. First series: t-BuN(CH2CH2)(2)O 1a > t-BuNEt2 Ib > t-BuNPr(2)(n)1c > t-BuN(CH2CH2OMe)(2) Id much greater than t-BuNBu2i le. Second series: t-(BuNBuMe)-Me-i 2a > t-(BuNPrMe)-Me-i 2b > t-(BuNBuEt)-Et-i 2c > t-(BuNBuPrn)-Pr-i 2d much greater than t-(BuNPrEt)-Et-i 2e. The reactivity of the corresponding borane adducts toward 1-octene increases in the reverse order. The following amines form highly reactive liquid borane adducts hydroborating 1-octene in tetrahydrofuran at room temperature in less than 1 h: t-BuN(CH2CH2OMe)(2), t-(BuNBuEt)-Et-i, and t-(BuNPrMe)-Me-i. The limit of borane complexation among the amines examined is reached for t-BuNBu2i exchanging borane neither with EMS nor with BH3-THF. Among the various borane adducts prepared, the more promising borane adducts, t-Bu(CH3OCH2CH2)(2)N-BH3 (7), t-(BuMePrN)-N-i-BH3 (8), and t-(BuEtBuN)-N-i-BH3 (9), were selected for complete hydroboration and reduction studies. Hydroboration studies with the new, highly reactive trialkylamine-borane adducts 7-9 and representative olefins, such as l-hexene, styrene, beta-pinene, cyclopentene, norbornene, cyclohexene, 2-methyl-2-butene, alpha-pinene, and 2,3-dimethyl-2-butene, in tetrahydrofuran, dioxane, tert-butyl methyl ether, n-pentane, and dichloromethane, at room temperature (22 +/- 3 degrees C) were carried out. The reactions are faster in dioxane, requiring 1-2 h for the hydroboration of simple, unhindered olefins to the trialkylborane stage. Moderately hindered olefins, such as cyclohexene and 2-methyl-2-butene, give the corresponding dialkylboranes rapidly, with further slow hydroboration. However, the more hindered olefins, alpha-pinene and 2,3-dimethyl-2-butene, give stable monoalkylboranes very rapidly, with further hydroboration proceeding relatively slowly. The hydroborations can also be carried out conveniently in other solvents, such as THF, tert-butyl methyl ether, and n-pentane. A significant; rate retardation is observed in dichloromethane. Regioselectivity studies of l-hexene and styrene using these amine-borane adducts show selectivities similar to that of BH3-THF. The rates and stoichiometry of the reaction of t-BuMePriN-BH3 in tetrahydrofuran with selected organic compounds containing representative functional groups were also examined at room temperature. The reductions of esters, amides, and nitriles, which exhibit a sluggish reaction at room temperature, proceed readily under reflux conditions in tetrahydrofuran and dioxane and without solvent (at 85-90 degrees C). The carrier amines can be recovered by simple acid-base manipulations in good yield and readily recycled to make the borane adducts.