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本文引用的文献

1
A Transition Metal Complex of D-Glucose.一种D-葡萄糖的过渡金属配合物。
Angew Chem Int Ed Engl. 2001 Nov 19;40(22):4210-4212. doi: 10.1002/1521-3773(20011119)40:22<4210::AID-ANIE4210>3.0.CO;2-Z.
2
Palladium-catalyzed enantioselective oxidation of chiral secondary alcohols: access to both enantiomeric series.钯催化手性仲醇的对映选择性氧化：获得两种对映体系列。
Angew Chem Int Ed Engl. 2008;47(34):6367-70. doi: 10.1002/anie.200801865.
3
Catalytic enantioselective stereoablative reactions: an unexploited approach to enantioselective catalysis.催化对映选择性立体消去反应：一种未被开发的对映选择性催化方法。
Org Biomol Chem. 2007 Nov 21;5(22):3571-6. doi: 10.1039/b711159m. Epub 2007 Oct 1.
4
Axially chiral NHC-Pd(II) complexes in the oxidative kinetic resolution of secondary alcohols using molecular oxygen as a terminal oxidant.使用分子氧作为终端氧化剂，轴向手性NHC-Pd(II)配合物用于仲醇的氧化动力学拆分。
Org Lett. 2007 Mar 1;9(5):865-8. doi: 10.1021/ol063061w. Epub 2007 Jan 30.
5
Origin of enantioselection in chiral alcohol oxidation catalyzed by Pd[(-)-sparteine]Cl2.Pd[(-)-鹰爪豆碱]Cl₂催化的手性醇氧化反应中对映选择性的起源。
J Am Chem Soc. 2005 Oct 26;127(42):14817-24. doi: 10.1021/ja053195p.
6
A practical synthesis of (+/-)-alpha-isosparteine from a tetraoxobispidine core.由四氧代双哌啶核心实现（±）-α-异鹰爪豆碱的实用合成。
Org Lett. 2005 Oct 13;7(21):4721-4. doi: 10.1021/ol0519184.
7
Evaluation of (+)-sparteine-like diamines for asymmetric synthesis.用于不对称合成的（+）-鹰爪豆碱类二胺的评估
J Org Chem. 2004 Aug 20;69(17):5789-92. doi: 10.1021/jo049182w.
8
A computational model relating structure and reactivity in enantioselective oxidations of secondary alcohols by (-)-sparteine-Pd(II) complexes.一种关于（-）-鹰爪豆碱-Pd（II）配合物对仲醇进行对映选择性氧化时结构与反应活性关系的计算模型。
J Am Chem Soc. 2004 Jun 30;126(25):7967-74. doi: 10.1021/ja031911m.
9
Highly selective asymmetric hydrogenation using a three hindered quadrant bisphosphine rhodium catalyst.使用三受阻象限双膦铑催化剂进行的高选择性不对称氢化反应。
J Am Chem Soc. 2004 May 19;126(19):5966-7. doi: 10.1021/ja048496y.
10
An experimentally derived model for stereoselectivity in the aerobic oxidative kinetic resolution of secondary alcohols by (sparteine)PdCl2.通过（鹰爪豆碱）PdCl₂对仲醇进行需氧氧化动力学拆分的立体选择性的实验推导模型。
J Am Chem Soc. 2004 Apr 14;126(14):4482-3. doi: 10.1021/ja039551q.

（鹰爪豆碱）二氯化钯的结构特征与反应活性：仲醇氧化动力学拆分中选择性的模型

Structural features and reactivity of (sparteine)PdCl2: a model for selectivity in the oxidative kinetic resolution of secondary alcohols.

作者信息

Trend Raissa M, Stoltz Brian M

机构信息

The Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, MC 164-30, Pasadena, California 91125, USA.

出版信息

J Am Chem Soc. 2008 Nov 26;130(47):15957-66. doi: 10.1021/ja804955e.

DOI:10.1021/ja804955e
PMID:18975867
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC2649720/
Abstract

The chiral ligand (-)-sparteine and PdCl(2) catalyze the enantioselective oxidation of secondary alcohols to ketones and thus effect a kinetic resolution. The structural features of sparteine that led to the selectivity observed in the reaction were not clear. Substitution experiments with pyridine derivatives and structural studies of the complexes generated were carried out on (sparteine)PdCl(2) and indicated that the C(1) symmetry of (-)-sparteine is essential to the location of substitution at the metal center. Palladium alkoxides were synthesized from secondary alcohols that are relevant steric models for the kinetic resolution. The solid-state structures of the alkoxides also confirmed the results from the pyridine derivative substitution studies. A model for enantioinduction was developed with C(1) symmetry and Cl(-) as key features. Further studies of the diastereomers of (-)-sparteine, (-)-alpha-iso- and (+)-beta-isosparteine, in the kinetic resolution showed that these C(2)-symmetric counterparts are inferior ligands in this stereoablative reaction [Mohr, J. T., Ebner, D. C., and Stoltz, B. M. Org. Biomol. Chem. 2007, 5, 3571-3576].

摘要

手性配体（-）-鹰爪豆碱与PdCl₂催化仲醇对映选择性氧化为酮，从而实现动力学拆分。导致该反应中观察到选择性的鹰爪豆碱的结构特征尚不清楚。对（鹰爪豆碱）PdCl₂进行了吡啶衍生物的取代实验以及所生成配合物的结构研究，结果表明（-）-鹰爪豆碱的C₁对称性对于金属中心的取代位置至关重要。由与动力学拆分相关的空间模型仲醇合成了钯醇盐。醇盐的固态结构也证实了吡啶衍生物取代研究的结果。以C₁对称性和Cl⁻为关键特征建立了对映体诱导模型。对（-）-鹰爪豆碱的非对映异构体（-）-α-异鹰爪豆碱和（+）-β-异鹰爪豆碱在动力学拆分中的进一步研究表明，在这种立体消除反应中，这些C₂对称的对应物是较差的配体[莫尔，J.T.，埃布纳，D.C.，和斯托尔兹，B.M.《有机生物分子化学》2007年，5，3571 - 3576]。