(S)-bis(3,5-diphenyl)(pyrrolidin-2-yl)methanol | 951008-56-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: (S)-bis(3,5-diphenyl)(pyrrolidin-2-yl)methanol
• 英文别名: bis(3,5-diphenylphenyl)-[(2S)-pyrrolidin-2-yl]methanol
• CAS: 951008-56-3
• 化学式: C₄₁H₃₅NO
• 分子量: 557.735
• InChiKey: BBMBNOOMBRYEOI-FAIXQHPJSA-N

物化性质

• 熔点：
  92-94 °C
• 沸点：
  776.8±50.0 °C(Predicted)
• 密度：
  1.148±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.2
• 重原子数：
  43
• 可旋转键数：
  7
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  32.3
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-bis(3,5-diphenyl)(pyrrolidin-2-yl)methanol 在 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 16.0h， 生成 [(2S)-2-[bis(3,5-diphenylphenyl)-hydroxymethyl]pyrrolidin-1-yl]-(4-pyrrolidin-1-ylpyridin-3-yl)methanone
  参考文献：
  名称：

  Nonenzymatic Acylative Kinetic Resolution of Baylis−Hillman Adducts

  摘要：

  The first efficient nonenzymatic acylative kinetic resolution of Baylis-Hillman adducts is reported. Chiral pyridine catalyst 1a and an optimized analogue 1e are capable of promoting the synthetically useful enantioselective acylation (the efficiency of which is outstanding for sp(2)-sp(2) carbinol substrates, s = 3.5-13.1, ee up to 97%) of Baylis-Hillman adducts derived from recalcitrant precursors which are currently difficult to synthesize utilizing benchmark asymmetric Baylis-Hillman reaction catalyst technology. A novel one-pot synthesis-kinetic resolution process involving a DBU-catalyzed Baylis-Hillman reaction and subsequent 1e/DBU-mediated enantioselective acylation has also been developed.

  DOI：

  10.1021/jo071223b
• 作为产物：
  描述：

  在 palladium on activated carbon 、 氢气 、 三氟乙酸 作用下， 以 甲醇 为溶剂， 以95 %的产率得到(S)-bis(3,5-diphenyl)(pyrrolidin-2-yl)methanol
  参考文献：
  名称：

  利用机器学习的有限实验数据：区分 Corey-Bakshi-Shibata 还原反应中的甲基和乙基

  摘要：

  我们提出了一个案例研究，介绍如何改进现有的无金属催化剂以应对特别困难的反应，即丁酮的 Corey-Bakshi-Shibata (CBS) 还原，这构成了能够区分甲基的经典和原型挑战来自乙基。由于没有已知的策略来应对这一挑战，我们利用机器学习的力量，构建了一个真实的（对于典型实验室）小型但高质量的数据集，其中包含约 100 个反应（一式三份运行）用于结合关键中间图（底物和催化剂）来训练模型，以预测对映体反应路径的吉布斯活化能 ΔΔ G ‡的差异。借助该模型，我们能够选择并随后筛选一小部分催化剂，并将丁酮 CBS 还原的选择性提高到 80% 对映体过量 (ee)，这是迄今为止该底物实现的最高可能值一种无金属催化剂，因此也超过了现有的最佳酶系统 (64% ee) 和 Corey 原始催化剂的选择性 (60% ee)。这意味着相对 Δ G ‡从 0.9 kcal mol –1 提高到 1.4 kcal

  DOI：

  10.1021/jacs.4c01286

文献信息

• CATALYST FOR ASYMMETRIC HYDROGENATION
  申请人：MAEDA Hironori

  公开号：US20100324338A1

  公开（公告）日：2010-12-23

  This invention aims at providing a catalyst for producing an optically active aldehyde or an optically active ketone, which is an optically active carbonyl compound, by carrying out selective asymmetric hydrogenation of an α,β-unsaturated carbonyl compound, particularly a catalyst which is insoluble in a reaction mixture for obtaining optically active citronellal which is useful as a flavor or fragrance, by carrying out selective asymmetric hydrogenation of citral, geranial or neral; and a method for producing a corresponding optically active carbonyl compound. The invention relates to a catalyst for asymmetric hydrogenation of an α,β-unsaturated carbonyl compound, which comprises a powder of at least one metal selected from metals belonging to Group 8 to Group 10 of the Periodic Table, or a metal-supported substance in which at least one metal selected from metals belonging to Group 8 to Group 10 of the Periodic Table is supported on a support, an optically active cyclic nitrogen-containing compound and an acid.

  这项发明旨在通过对α，β-不饱和羰基化合物进行选择性不对称加氢，特别是通过对柠檬醛、香叶醛或柠檬醛进行选择性不对称加氢，从而提供用作香料或香精的有用的光学活性香茅醛的催化剂，该香茅醛是一种光学活性羰基化合物；以及生产相应的光学活性羰基化合物的方法。该发明涉及一种用于不对称加氢α，β-不饱和羰基化合物的催化剂，其包括来自周期表第8至第10族金属中至少一种金属的粉末，或者至少一种来自周期表第8至第10族金属的金属负载物质，该金属负载在一种支撑物上，还包括光学活性的含氮环化合物和酸。
• Chiral Pyridoxal-Catalyzed Asymmetric Biomimetic Transamination of α-Keto Acids
  作者：Limin Shi、Chuangan Tao、Qin Yang、Yong Ethan Liu、Jing Chen、Jianfeng Chen、Jiaxin Tian、Feng Liu、Bo Li、Yongling Du、Baoguo Zhao

  DOI：10.1021/acs.orglett.5b02895

  日期：2015.12.4

  A series of chiral pyridoxals 8 and 9 have been developed from commercially available pyridoxine and (S)-alpha,alpha-diarylprolinols. The pyridoxals exhibited good catalytic activity in an asymmetric transamination of alpha-keto acids with 2,2-diphenylglycine (7f) as the amine source to give various alpha-amino acids in 29-85% yields with 53-80% ee's. The current asymmetric transamination has successfully mimicked a complete biological transamination process characterized by two half-transaminations, a small chiral pyridoxal molecule acting as the catalyst, and enantioselective control.
• US8217204B2
  申请人：——

  公开号：US8217204B2

  公开（公告）日：2012-07-10
• Nonenzymatic Acylative Kinetic Resolution of Baylis−Hillman Adducts
  作者：Ciarán Ó Dálaigh、Stephen J. Connon

  DOI：10.1021/jo071223b

  日期：2007.8.31

  The first efficient nonenzymatic acylative kinetic resolution of Baylis-Hillman adducts is reported. Chiral pyridine catalyst 1a and an optimized analogue 1e are capable of promoting the synthetically useful enantioselective acylation (the efficiency of which is outstanding for sp(2)-sp(2) carbinol substrates, s = 3.5-13.1, ee up to 97%) of Baylis-Hillman adducts derived from recalcitrant precursors which are currently difficult to synthesize utilizing benchmark asymmetric Baylis-Hillman reaction catalyst technology. A novel one-pot synthesis-kinetic resolution process involving a DBU-catalyzed Baylis-Hillman reaction and subsequent 1e/DBU-mediated enantioselective acylation has also been developed.
• 10.1021/jacs.4c01286
  作者：Pereira, Oliver、Ruth, Marcel、Gerbig, Dennis、Wende, Raffael C.、Schreiner, Peter R.

  DOI：10.1021/jacs.4c01286

  日期：——

  a particularly difficult reaction, namely, the Corey–Bakshi–Shibata (CBS) reduction of butanone, which constitutes the classic and prototypical challenge of being able to differentiate a methyl from an ethyl group. As there are no known strategies on how to address this challenge, we leveraged the power of machine learning by constructing a realistic (for a typical laboratory) small, albeit high-quality

  我们提出了一个案例研究，介绍如何改进现有的无金属催化剂以应对特别困难的反应，即丁酮的 Corey-Bakshi-Shibata (CBS) 还原，这构成了能够区分甲基的经典和原型挑战来自乙基。由于没有已知的策略来应对这一挑战，我们利用机器学习的力量，构建了一个真实的（对于典型实验室）小型但高质量的数据集，其中包含约 100 个反应（一式三份运行）用于结合关键中间图（底物和催化剂）来训练模型，以预测对映体反应路径的吉布斯活化能 ΔΔ G ‡的差异。借助该模型，我们能够选择并随后筛选一小部分催化剂，并将丁酮 CBS 还原的选择性提高到 80% 对映体过量 (ee)，这是迄今为止该底物实现的最高可能值一种无金属催化剂，因此也超过了现有的最佳酶系统 (64% ee) 和 Corey 原始催化剂的选择性 (60% ee)。这意味着相对 Δ G ‡从 0.9 kcal mol –1 提高到 1.4 kcal