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化学进展 2022, Vol. 34 Issue (7): 1537-1547 DOI: 10.7536/PC220221 前一篇   后一篇

• 综述 •

手性催化与合成中的一些凝聚态化学问题

蒋茹, 刘晨旭, 杨平, 游书力*()   

  1. 中国科学院上海有机化学研究所 金属有机化学国家重点实验室 上海 200032
  • 收稿日期:2022-02-17 修回日期:2022-04-07 出版日期:2022-07-24 发布日期:2022-06-20
  • 通讯作者: 游书力
  • 基金资助:
    国家自然科学基金项目(91856201)
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Condensed Matter Chemistry in Asymmetric Catalysis and Synthesis

Ru Jiang, Chenxu Liu, Ping Yang, Shuli You()   

  1. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,Shanghai 200032, China
  • Received:2022-02-17 Revised:2022-04-07 Online:2022-07-24 Published:2022-06-20
  • Contact: Shuli You
  • Supported by:
    National Natural Science Foundation of China(91856201)

凝聚态化学作为一门研究化学反应中凝聚态物质的科学,最近引起了化学界的广泛关注。从手性化学角度出发,本文列举了近年来手性催化与合成中的一些凝聚态化学现象,分类介绍了不对称催化反应中不同类型的凝聚态物质,并通过列举实例分析讨论了凝聚态物质的具体组成、层次结构等因素对反应的催化活性、对映及区域选择性控制影响,以望能引起业界对凝聚态科学的关注,启发更多学者从凝聚态化学角度思考有机化学反应本质并解决相关问题,完善凝聚态科学体系。

关键词： 凝聚态, 手性催化, 对映选择性, 非线性效应, 溶剂效应, 相转移催化, 对映体自歧化

Condensed matter chemistry, as a science of studying condensed matter in chemical reactions, has attracted extensive attention recently. In this review, condensed matter chemistry related to asymmetric catalysis and synthesis are briefly summarized, and different condensed matter phenomena in asymmetric catalytic reactions were classified. Besides, relative works were discussed in detail to illustrate the effects of the multi-level structures and composition of condensed matter on the catalytic activity, enantio- and regioselective control. It is hoped that the system of condensed matter science would be well developed by attracting more attention and bringing more thoughts to the essence of reaction from the perspective of condensed matter chemistry.

Contents

1 Introduction

2 Chirality and asymmetric catalysis

2.1 Importance of chirality

2.2 Asymmetric catalysis

3 Condensed matter chemistry in asymmetric catalysis and synthesis

3.1 Condensation of catalysts: nonlinear effect

3.2 Condensation of catalysts and solvents

3.3 Condensation of catalysts and additives

3.4 Condensation of catalysts and substrates: phase-transfer catalysis

3.5 Condensation of enantiomers: SDE

4 Conclusion and outlook

Key words: condensed state, asymmetric catalysis, enantioselectivity, nonlinear effect, solvent effect, phase-transfer catalysis, self-disproportionation of enantiomers
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图1 不对称催化与合成中的非线性效应[5]
Fig. 1 Nonlinear effects in asymmetric catalysis and synthesis[5]
图式1 二烷基锌对醛的高对映选择性加成反应[7]
Scheme 1 Highly enantioselective addition of dialkylzincs to aldehydes[7]
图式2 反应机理[8]
Scheme 2 Reaction mechanism[8]
图式3 手性放大效应与形成机理[8⇓~10]
Scheme 3 Asymmetric amplification and related mechanism[8⇓~10]
图式4 (l)-脯氨酸催化的不对称反应[11,12]
Scheme 4 (l)-Proline-catalyzed asymmetric reactions[11,12]
图2 固-液相共存时脯氨酸催化的非线性行为[13]
Fig. 2 Nonlinearity of proline catalysis under heterogeneous conditions[13]
图式5 反应时长依赖的对映发散性合成[16,17]
Scheme 5 Time-dependent enantiodivergent synthesis via sequential kinetic resolution[16,17]
图式6 金属铱催化Z式保留不对称烯丙基取代反应[17]
Scheme 6 Iridium-catalyzed Z-retentive asymmetric allylic substitution reactions[17]
图式7 双配体配位的铱配合物的合成与表征[18]
Scheme 7 Synthesis and characterization of π-allyl iridium(Ⅲ) complexes[18]
表1 铜催化对映选择性吲哚与亚苄基丙二酸酯的Friedel-Crafts反应[25,26]
Table 1 Enantioselective Friedel-Crafts reaction between indoles and alkylidene malonates catalyzed by copper(Ⅱ) complexes[25,26]
entry Ligand/Cu solvent temperature
(℃)		 time (h) yield
(%)		 ee
1 1/1.5 CHCl2CHCl2 0 22 86 80% (R)
2 1.2/1 THF 15 64 5 81% (S)
3 1.2/1 MeOH 15 5 90 48% (S)
4 1.2/1 EtOH 15 3 90 63% (S)
5 1.2/1 iPrOH 15 2 99 88% (S)
6 1.2/1 iBuOH 15 3 99 90% (S)
图3 立体化学控制模型[26]
Fig. 3 Stereochemical models[26]
图式8 均相与异相催化体系下的正交对映选择性吲哚Friedel-Crafts烷基化反应[28]
Scheme 8 Orthogonal enantioselectivity approaches using homogeneous and heterogeneous catalyst systems: Friedel-Crafts alkylation of indole[28]
图4 立体化学模型预测:(a)均相催化体系;(b)异相催化体系[28]
Fig. 4 Proposed stereochemical models for (a) homogeneous, and (b) heterogeneous systems[28]
图5 手性阳离子相转移催化剂示意图[32]
Fig. 5 Chiral cation phase-transfer catalyst[32]
图6 手性阳离子相转移催化反应机理[32]
Fig. 6 Mechanism of chiral cation phase-transfer catalysis reaction[32]
图式9 第一例相转移催化反应[33]
Scheme 9 The first example of phase-transfer catalysis[33]
图7 相转移催化剂催化氰基化反应机理[33]
Fig. 7 Mechanism of cyanation reaction via chiral phase-transfer catalysis[33]
图式10 首例不对称相转移反应[34]
Scheme 10 The first example of asymmetric phase-transfer catalysis reaction[34]
图式11 手性阴离子相转移催化不对称亲电氟化反应[35]
Scheme 11 Asymmetric electrophilic fluorination via chiral anion phase-transfer catalysis[35]
图8 手性阴离子相转移反应机理[35]
Fig. 8 Mechanism of chiral anion phase-transfer catalysis reaction[35]
图9 对映体自歧化的原理[37]
Fig. 9 The principle of enantiomeric self-disproportionation[37]
表2 β-胺基酯类化合物在非手性柱上的对映体自歧化[36]
Table 2 Self-disproportionation of enantiomers of β-amino acid esters on achiral silica gel chromatography[36]
Compound Starting ee (%) Eluent ee (%) min ee (%) max
A 95.0 Hex/EtOAc = 5∶1 83.3 99.9
31.1 Hex/EtOAc = 5∶1 20.9 41.8
66.6 Hex/EtOAc = 5∶1 8.1 99.9
66.6 Hex/E2O = 1∶1 54.8 99.9
66.6 CHCl3 65.5 68.2
B 66.6 Hex/EtOAc = 5∶1 58.4 99.9
C 66.6 Hex/EtOAc = 5∶1 59.9 78.8
图10 非手性柱层析时的对映体自歧化[36,39]
Fig. 10 Self-disproportionation of enantiomers on achiral silica gel chromatography[36,39]
图11 消旋1,2-二氢异喹啉衍生物的堆积结构[39]
Fig. 11 Packing structure of racemic 1, 2-dihydroisoquinolines derivative[39]
图12 对映体化合物在蒸馏过程中自聚集[42]
Fig. 12 Self-disproportionation of enantiomers during distillation[42]
图13 对映体化合物在升华过程中自聚集[43,44]
Fig. 13 Self-disproportionation of enantiomers during sublimation[43,44]
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