(4R,5R)-2-(9-Fluorenylidene)-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanol | 126524-75-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: (4R,5R)-2-(9-Fluorenylidene)-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanol
• 英文别名: (4R,trans)-α,α,α',α'-tetraphenylspiro{1,3-dioxolane-2,9'-(9H)-fluorene}-4,5-dimethanol；[(4R,5R)-5-[hydroxy(diphenyl)methyl]spiro[1,3-dioxolane-2,9'-fluorene]-4-yl]-diphenylmethanol
• CAS: 126524-75-2
• 化学式: C₄₁H₃₂O₄
• 分子量: 588.703
• InChiKey: WWQOWHHJLANXKL-XPSQVAKYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  45
• 可旋转键数：
  6
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4R,5R)-2-(9-Fluorenylidene)-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanol 在 三乙胺 、 三氯化磷 作用下， 以 四氢呋喃 为溶剂， 以1.77 g的产率得到(3a'R,8a'R)-6'-chloro-4',4',8',8'-tetraphenyl-3a',4',8',8a'-tetrahydrospiro[fluorene-9,2'-[1,3]dioxolo[4,5-e][1,3,2]dioxaphosphepine]
  参考文献：
  名称：

  镍 (0) - 催化末端丙二烯的氢氰化：支链烯丙腈的区域选择性和对映选择性方法

  摘要：

  本文报道了高度支化的区域选择性镍 (0) 催化的单取代和 1,1-二取代丙二烯的氢氰化以及 1,1-二取代丙二烯的不对称氢氰化，从而获得支化的叔和季 β,γ-烯丙基腈类。对于末端丙二烯的区域选择性氢氰化，镍 (0)/Biphephos 催化体系适用于包含酯、THP 基团、伯脂肪族碘化物和游离羧酸等官能团的底物范围，提供高达 96% 的产率。通过将基于 Ni(0)/TADDOL 的双亚磷酸酯催化剂应用于 1,1-二取代丙二烯的催化体系，支链季烯丙基腈的收率高达 99%，对映选择性高达 86%。这两种协议都利用了可管理的 HCN 源并证明了良好的原子经济性。此外，

  DOI：

  10.1002/adsc.202201189
• 作为产物：
  描述：

  溴苯 、 (R,R)-Dimethyl O,O-fluorenylidenetartrate 在 magnesium 作用下， 生成 (4R,5R)-2-(9-Fluorenylidene)-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanol
  参考文献：
  名称：

  On the Ti-TADDOLate-Catalyzed Diels-Alder Addition of 3-Butenoyl-1,3-oxazolidin-2-one to Cyclopentadiene. General Features of Ti-BINOLate- and Ti-TADDOLate-Mediated Reactions

  摘要：

  A systematic investigation of the enantioselective Diels-Alder addition of 3-butenoyl-1,3-oxazolidin-2-one to cyclopentadiene under the influence of catalytic amounts of dichloro-Ti complexes of alpha,alpha,alpha',alpha'-tetraaryl-1,3-dioxolane-4,5-dimethanols (TADDOLs) is described. The influence of the mode of catalyst preparation, amount of catalyst, presence of molecular sieves, concentration of the reactands temperature, solvent, and TADDOL structure on this reaction is studied. Best results (enantiomer ratio er 94:6) are obtained with the TADDOL-bearing Arl = C6H5 and C6H5/CH3 substituents in the dioxolane 2-position (47) and with the C-2-symmetrical TADDOL with Arl = 2-naphthyl and two CH3 groups on the dioxolane 2-position (16). A surprising reversal of the absolute topicity of the reaction is observed with TADDOLs (15, 28, 32, 38) bearing four 1-naphthyl groups: the 2(R)- instead of the 2(S)-bicyclo[2.2.1]hept-5-en-2-carboxylic acid derivatives are formed with enantioselectivities of up to 86:14. The crystal structures of several TADDOLs (16, 28, 47) and of the tetracyclohexylanalog 50 are described and compared with previously determined structures. A superposition of 29 structures reveals that the cyclic array of atoms of the TADDOLate moiety always has two axial and two equatorial aryl groups in a lambda-type conformation when derived from (RP)-tartrate and in a delta-type conformation when derived from(S,S)-tartrate. The binaphthols (BINOLs) show similar structural features (lambda in (P) or (S) and delta in (M) or (R) enantiomers). A mnemonic rule is disclosed which applies to the steric course of Ti-BINOLate- and Ti-TADDOLate-mediated reactions involving monodentate and bidentate electrophiles. The possible structure of the reactive complex involved in enantioselective reactions mediated by Ti-BINOLates and -TADDOLates, i.e., inter- and intramolecular [2 + 2] and [4 + 2] cycloadditions and ene reactions, is discussed.

  DOI：

  10.1021/jo00111a042
• 作为试剂：
  描述：

  苯乙酮 在 aluminium hydride 、 (4R,5R)-2-(9-Fluorenylidene)-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanol 作用下， 以 四氢呋喃 为溶剂， 生成 苏合香醇
  参考文献：
  名称：

  摘要：

  Prochiral substrates (alkyl aryl ketones, cyclopropyl methyl ketone, 1-indanone, 1-tetralone, ethyl 2-oxo-4-phenylbutyrate, and N-(diphenylphosphinyl)acetophenoneimine) were subjected to asymmetric reduction with aluminum hydride reagents, which were prepared by modifications of NaAlH4 or AlH3 with chiral alpha,alpha,alpha',alpha'-tetraaryl-1,3-dioxolane-4,5-dimethanols (TADDOL). The effects of the nature of the substituents in TADDOL, the structure of the prochiral substrate, and the reaction conditions on the stereochemistry of reduction were investigated. The highest enantioselectivity (70-90% ee) was achieved upon reduction of alkyl aryl ketones and N-(diphenylphosphinyl)acetophenoneimine with NaAl(TADDOLate)H-2 in THF or diglyme at a temperature from -70 to -20 degreesC. The mechanism of asymmetric induction in the reduction reactions of ketones with aluminum hydride reagents is discussed. The stereochemical results of reduction were explained by comparing three-dimensional models of the most probable transition states.

  DOI：

  10.1023/a:1023443807540

文献信息

• Hafner, Andreas; Duthaler, Rudolf O.; Marti, Roger, Journal of the American Chemical Society, 1992, vol. 114, # 7, p. 2321 - 2336
  作者：Hafner, Andreas、Duthaler, Rudolf O.、Marti, Roger、Rihs, Grety、Rothe-Streit, Petra、Schwarzenbach, Franz

  DOI：——

  日期：——
• US6166260A
  申请人：——

  公开号：US6166260A

  公开（公告）日：2000-12-26
• On the Ti-TADDOLate-Catalyzed Diels-Alder Addition of 3-Butenoyl-1,3-oxazolidin-2-one to Cyclopentadiene. General Features of Ti-BINOLate- and Ti-TADDOLate-Mediated Reactions
  作者：Dieter Seebach、Robert Dahinden、Roger E. Marti、Albert K. Beck、Dietmar A. Plattner、Florian N. M. Kuehnle

  DOI：10.1021/jo00111a042

  日期：1995.3

  A systematic investigation of the enantioselective Diels-Alder addition of 3-butenoyl-1,3-oxazolidin-2-one to cyclopentadiene under the influence of catalytic amounts of dichloro-Ti complexes of alpha,alpha,alpha',alpha'-tetraaryl-1,3-dioxolane-4,5-dimethanols (TADDOLs) is described. The influence of the mode of catalyst preparation, amount of catalyst, presence of molecular sieves, concentration of the reactands temperature, solvent, and TADDOL structure on this reaction is studied. Best results (enantiomer ratio er 94:6) are obtained with the TADDOL-bearing Arl = C6H5 and C6H5/CH3 substituents in the dioxolane 2-position (47) and with the C-2-symmetrical TADDOL with Arl = 2-naphthyl and two CH3 groups on the dioxolane 2-position (16). A surprising reversal of the absolute topicity of the reaction is observed with TADDOLs (15, 28, 32, 38) bearing four 1-naphthyl groups: the 2(R)- instead of the 2(S)-bicyclo[2.2.1]hept-5-en-2-carboxylic acid derivatives are formed with enantioselectivities of up to 86:14. The crystal structures of several TADDOLs (16, 28, 47) and of the tetracyclohexylanalog 50 are described and compared with previously determined structures. A superposition of 29 structures reveals that the cyclic array of atoms of the TADDOLate moiety always has two axial and two equatorial aryl groups in a lambda-type conformation when derived from (RP)-tartrate and in a delta-type conformation when derived from(S,S)-tartrate. The binaphthols (BINOLs) show similar structural features (lambda in (P) or (S) and delta in (M) or (R) enantiomers). A mnemonic rule is disclosed which applies to the steric course of Ti-BINOLate- and Ti-TADDOLate-mediated reactions involving monodentate and bidentate electrophiles. The possible structure of the reactive complex involved in enantioselective reactions mediated by Ti-BINOLates and -TADDOLates, i.e., inter- and intramolecular [2 + 2] and [4 + 2] cycloadditions and ene reactions, is discussed.
• Nickel(0)‐Catalyzed Hydrocyanation of Terminal Allenes: A Regio‐ and Enantioselective Approach to Branched Allylic Nitriles
  作者：Timm Bury、Sven Kullmann、Bernhard Breit

  DOI：10.1002/adsc.202201189

  日期：2023.2.7

  A highly branched regioselective nickel(0)-catalyzed hydrocyanation of mono- and 1,1-disubstituted allenes as well as an asymmetric hydrocyanation of 1,1-disubstituted allenes are reported herein, giving access to branched tertiary and quaternary β,γ-allylic nitriles. For the regioselective hydrocyanation of terminal allenes, a nickel(0)/Biphephos catalytic system applicable to a substrate scope containing

  本文报道了高度支化的区域选择性镍 (0) 催化的单取代和 1,1-二取代丙二烯的氢氰化以及 1,1-二取代丙二烯的不对称氢氰化，从而获得支化的叔和季 β,γ-烯丙基腈类。对于末端丙二烯的区域选择性氢氰化，镍 (0)/Biphephos 催化体系适用于包含酯、THP 基团、伯脂肪族碘化物和游离羧酸等官能团的底物范围，提供高达 96% 的产率。通过将基于 Ni(0)/TADDOL 的双亚磷酸酯催化剂应用于 1,1-二取代丙二烯的催化体系，支链季烯丙基腈的收率高达 99%，对映选择性高达 86%。这两种协议都利用了可管理的 HCN 源并证明了良好的原子经济性。此外，