3,3'-Bis[tert-butyl(dimethyl)silyl][1,1'-binaphthalene]-2,2'-diol | 1018784-91-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 3,3'-Bis[tert-butyl(dimethyl)silyl][1,1'-binaphthalene]-2,2'-diol
• 英文别名: 3-[tert-butyl(dimethyl)silyl]-1-[3-[tert-butyl(dimethyl)silyl]-2-hydroxynaphthalen-1-yl]naphthalen-2-ol
• CAS: 1018784-91-2；190661-84-8；119707-85-6
• 化学式: C₃₂H₄₂O₂Si₂
• 分子量: 514.855
• InChiKey: HJHCQOWIMGPCKV-UHFFFAOYSA-N

物化性质

• 沸点：
  545.7±50.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.5
• 重原子数：
  36
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,3'-Bis[tert-butyl(dimethyl)silyl][1,1'-binaphthalene]-2,2'-diol 、 六氯化钨 以 甲苯 为溶剂， 生成 Δ-(S*,S*,S*)-tris(1,1'-binaphthol-2,2'-diolato)tungsten(VI)
  参考文献：
  名称：

  Dietz, Steven D.; Eilerts, Nancy W.; Heppert, Joseph A., Inorganic Chemistry, 1993, vol. 32, # 9, p. 1698 - 1705

  摘要：

  DOI：
• 作为产物：
  描述：

  3,3'-Dibromo-2,2'-bis-(tert-butyl-dimethyl-silanyloxy)-[1,1']binaphthalenyl 在 叔丁基锂 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 30.0h， 以87%的产率得到3,3'-Bis[tert-butyl(dimethyl)silyl][1,1'-binaphthalene]-2,2'-diol
  参考文献：
  名称：

  空间位阻手性联萘酚衍生物的高效合成

  摘要：

  已经描述了一种制备各种空间位阻手性联萘酚衍生物的高效方法，该方法涉及手性 3,3'-二溴-1,1'-bi-2 的双（三烷基甲硅烷基醚）的分子内 1,3-重排-萘酚与 t-BuLi。

  DOI：

  10.1246/bcsj.61.2975

文献信息

• Enantioselective Oxidative (4+3) Cycloadditions between Allenamides and Furans through Bifunctional Hydrogen-Bonding/Ion-Pairing Interactions
  作者：Laura Villar、Uxue Uria、Jose I. Martínez、Liher Prieto、Efraim Reyes、Luisa Carrillo、Jose L. Vicario

  DOI：10.1002/anie.201704804

  日期：2017.8.21

  N‐trifluoromethanesulfonyl phosphoramides catalyze the enantioselective (4+3) cycloaddition between furans and oxyallyl cations, the latter being generated in situ by oxidation of allenamides. The chiral organic phosphoramide counteranion is proposed to engage in the activation of the oxyallyl cation intermediate through cooperative hydrogen‐bonding and ion‐pairing interactions, enabling an efficient chirality

  基于BINOL的N-三氟甲磺酰基磷酰胺可催化呋喃和氧烯丙基阳离子之间的对映选择性（4 + 3）环加成反应，后者是通过烯丙酰胺的氧化而原位生成的。提议使用手性有机磷酰胺抗衡阴离子，通过协同氢键和离子对相互作用参与羟基烯丙基阳离子中间体的活化，从而实现有效的手性转移，从而为最终的加合物提供高非对映和对映选择性。值得注意的是，该反应显示出广泛的底物范围，包括各种取代的烯丙酰胺和呋喃。
• Group 5 Metal Binaphtholate Complexes for Catalytic Asymmetric Hydroaminoalkylation and Hydroamination/Cyclization
  作者：Alexander L. Reznichenko、Thomas J. Emge、Stephan Audörsch、Eric G. Klauber、Kai C. Hultzsch、Bernd Schmidt

  DOI：10.1021/om1011006

  日期：2011.3.14

  3,3'-Silylated binaphtholate tantalum and niobium complexes were shown to be efficient catalysts for the asymmetric hydroaminoalkylation of N-methylaniline derivatives and N-benzylmethylamine with simple alkenes in enantioselectivities of up to 80% ee. No hydroaminoalkylation was observed with aminoalkenes; rather, exclusive asymmetric hydroamination/cyclization took place in up to 81% ee.
• Kinetics and thermodynamics of intra- and intermolecular rearrangement in binaphtholate complexes of titanium(IV)
  作者：Timothy J. Boyle、Denise L. Barnes、Joseph A. Heppert、Luis Morales、Fusao Takusagawa、John C. Connolly

  DOI：10.1021/om00039a017

  日期：1992.3

  3,3'-Disubstituted-1,1'-bi-2-naphthols (H2R2BINO where R = Me or SiMe2-t-Bu) react with Ti(O-i-Pr)4 to produce molecules of empirical formula [(R2BINO)Ti(O-i-Pr)2]n. Analytical methods including NMR spectroscopy, molecular weight cryoscopy, and X-ray crystallography were used to identify the (t-BuMe2Si)2BINO-substituted complex as a monomer and the Me2BINO-substituted complex as a dimer. This dinuclear complex possesses a highly distorted edge-fused trigonal-bipyramidal structure, whose 1,3-Ti2O2 core is bridged by two naphthoxide units. There is a distinct thermodynamic preference for the incorporation of ligands of like chirality into the dimer. A second set of complexes having empirical formula (R2BINO)Ti2(O-i-Pr)6 (R = Me, SiMe2-t-Bu) are accessible through either the reaction of 2 equiv of Ti(O-i-Pr)4 with H2R2BINO or a reaction between [(R2BINO)Ti(O-i-Pr)2]n and Ti(O-i-Pr)4. The (Me2BINO)Ti2(O-i-Pr)6 complex possesses C1 symmetry at the low-temperature limit, implying that the molecule adopts an edge-fused trigonal-bipyramidal structure bridged by one naphthoxide and one isopropoxide ligand. At higher temperatures, a fluxional process, (DELTA-G double-ended dagger 240 = 10.8 kcal/mol) generates time-averaged C2 symmetry consistent with the rupture of the isopropoxide bridge to produce a binaphtholate ligand bound to two ''Ti(O-i-Pr)3'' units. (t-BuMe2Si)2BINO}Ti2(O-i-Pr)6 adopts this C2-symmetric structure in both solution and the solid state. Both the (Me2BINO)Ti2(O-i-Pr)6 and (t-BuMe2Si)2BINO}Ti2(O-i-Pr)6 complexes display temperature-dependent equilibria in solution between Ti(O-i-Pr)4 and either [(Me2BINO)Ti(O-i-Pr)2]2 or (t-BuMe2Si)2BINO}Ti(O-i-Pr)2, respectively. The thermodynamic characteristics of these equilibria follow: Me2BINO, DELTA-H-degrees = -12.5 +/- 0.6 kcal/mol, DELTA-S-degrees = 38 +/- 2 eu; (t-BuMe2Si)2BINO, DELTA-H-degrees = -12.0 +/- 0.8 kcal/mol, DELTA-S-degrees = -44 +/- 4 eu. The (Me2BINO)Ti2(O-i-Pr)6 complex also engages in an independent intermolecular exchange processes in which a ''Ti(O-i-Pr)4'' unit is exchanged with free Ti(O-i-Pr)4 in solution (DELTA-H double-ended dagger = 14.1 +/- 0.9 kcal/mol, DELTA-S double-ended dagger = -2 +/- 2 eu). When compared with the previously observed fluxional process in (Me2BINO)Ti2(O-i-Pr)6, this observation demonstrates that polynuclear titanium complexes can engage in distinct intramolecular and intermolecular exchange processes. Crystal data for (t-BuMe2Si)2BINO}Ti(O-i-Pr)2 at 113 K: a = 10.866 (3) angstrom, b = 15.572 (4) angstrom, c = 23.059 (4) angstrom, beta = 93.76 (2)-degrees, Z = 4, D(calc) = 1.152, space group P2(1)/c, R(F) = 0.037, R(W)(F) = 0.051 for 3861 reflections. Crystal data for [(Me2BINO)Ti(O-i-Pr)2]2 at 106 K: a = 17.728 (3) angstrom, b = 11.079 (4) angstrom, c = 26.232 (4) angstrom, beta = 101.00 (3)-degrees, Z = 4, D(calc) = 1.257, space group P2(1)/c, R(F) = 0.069, R(W)(F) = 0.077 for 3231 reflections. Crystal data for (t-BuMe2Si)2BINO}Ti2(O-i-Pr)6 at 113 K: a = 14.444 (2) angstrom, b = 18.676 (3) angstrom, c = 20.788 (4) angstrom, beta = 98.76 (2)-degrees, Z = 4, D(calc) = 1.143, space group C2/c, R(F) = 0.059, R(W)(F) = 0.091 for 2860 reflections.
• MARUOKA, KEIJI;ITOH, TAKAYUKI;ARAKI, YOSHITAKA;SHIRASAKA, TADASHI;YAMAMOT+, BULL. CHEM. SOC. JAP., 61,(1988) N 8, C. 2975-2976
  作者：MARUOKA, KEIJI、ITOH, TAKAYUKI、ARAKI, YOSHITAKA、SHIRASAKA, TADASHI、YAMAMOT+

  DOI：——

  日期：——
• Efficient Synthesis of Sterically Hindered Chiral Binaphthol Derivatives
  作者：Keiji Maruoka、Takayuki Itoh、Yoshitaka Araki、Tadashi Shirasaka、Hisashi Yamamoto

  DOI：10.1246/bcsj.61.2975

  日期：1988.8

  A highly effective method for preparation of a variety of sterically hindered chiral binaphthol derivatives has been described which involves the intramolecular 1,3-rearrangement of bis(trialkylsilyl ether) of chiral 3,3′-dibromo-1,1′-bi-2-naphthol with t-BuLi.

  已经描述了一种制备各种空间位阻手性联萘酚衍生物的高效方法，该方法涉及手性 3,3'-二溴-1,1'-bi-2 的双（三烷基甲硅烷基醚）的分子内 1,3-重排-萘酚与 t-BuLi。