手性硅醇的不对称催化构建研究

硅醇在有机合成中具有重要的应用。硅醇既可以作为偶联试剂和导向基团，也可以作为氢键和阴离子结合的催化剂。同时，硅醇作为药物和生物活性分子的合成中间体被广泛应用。硅醇的另一个重要应用是作为合成含硅聚合物的单体。近年来，手性有机硅化合物的构建取得了快速的发展。然而，手性硅醇的催化不对称合成仍然具有挑战性。本论文主要发展了铑催化二氢硅烷的不对称水解氧化反应，首次实现了结构多样化的手性硅醇及双硅醇的不对称催化构建。该反应条件温和、官能团兼容性好，以H₂O为氧化剂，H₂为唯一的副产物，具有优异的化学和立体选择性。主要内容如下：

该反应以[Rh(cod)Cl]₂和手性双膦配体为催化体系，二氢硅烷和水为反应底物，在温和条件下发生水氧化反应，以60-95%的收率和63-97%的对映体过量值生成手性硅醇。该反应对三氟甲基、卤原子、烷氧基、胺基、不饱和双键、缩醛等官能团有很好的耐受性。含苯并呋喃、噻吩、咔唑、吡啶等杂环，及香叶醇、雌二醇、呋喃糖苷、石胆酸等复杂天然产物分子骨架的底物也适用于该反应。值得注意的是，该反应只对二氢硅烷起作用，对一氢硅烷不起作用，具有独特的化学选择性。该反应还可以合成一系列手性双硅醇化合物，具有较高的产率（57-93%）、对映选择性（> 99% ee）和非对映选择性（8.6:1-48:1）。这些具有Si−H和Si−OH基团的手性双硅醇化合物可作为特殊单体应用于新型手性硅基材料的构建。手性硅醇产物通过两步高效立体专一性转化可以得到硅基膦配体和硅基氮配体，手性硅醇产物和烯烃发生硅氢化反应高效地得到硅替药物分子对氟-硅-六氢-地芬尼多的衍生物。另外，通过氘代实验及动力学实验对反应机理进行了初步的探索，结果表明二氢硅烷对Rh−H的氧化加成及随后的脱氢气步骤为可逆过程，H₂O参与Rh−Si中间体的𝜎−复分解过程为反应的决速步骤。

[1] E LIEL E L, WILEN S H, MANDER L N. Stereochemistry of Organic Compounds[M]. 1994.
[2] RIEHL J P, EDITOR. Mirror-Image Asymmetry: An Introduction to the Origin and Consequences of Chirality[M]. 2010.
[3] IGAWA K, TOMOOKA K. IGAWA K. Chiral Silicon Molecules, In Organosilicon Chemistry: Novel Approaches and Reactions[M]. Weinheim: Wiley, Germany, 2019:495-532.
[4] TREGUER P, NELSON D M, VAN BENNEKOM A J, et al. The Silica Balance in the World Ocean: A Reestimate[J]. Science, 1995, 268(5209): 375-379.
[5] (a) CHEN J W, CAO Y. Silole-Containing Polymers: Chemistry and Optoelectronic Properties[J]. Macromolecular Rapid Communications, 2007, 28(17): 1714-1742. (b) KAMINO B A, BENDER T P. The Use of Siloxanes, Silsesquioxanes, and Silicones in Organic Semiconducting Materials[J]. Chemical Society Reviews, 2013, 42(12): 5119-5130. (c) 冯豪豪. 三种稠环电子受体材料的分子工程与光伏性能研究[D]. 江苏:南京理工大学,2019.
[6] (a) LANGKOPF E, SCHINZER D. Uses of Silicon-Containing Compounds in the Synthesis of Natural Products[J]. Chemical Society Reviews, 1995, 95(5): 1375-1408. (b) CHAN T H, FLEMING I. Electrophilic Substitution of Organosilicon Compounds - Applications to Organic Synthesis[J]. Synthesis, 1979(10): 761-786. (c) DENMARK S E, LIU J H C. Silicon-Based Cross-Coupling Reactions in the Total Synthesis of Natural Products[J]. Angewandte Chemie International Edition, 2010, 49(17): 2978-2986. (d) KLARE H F T, ALBERS L, SUESSE L, et al. Silylium Ions: From Elusive Reactive Intermediates to Potent Catalysts[J]. Chemical Society Reviews, 2021, 121(10): 5889-5985.
[7] (a) FRANZ A K, WILSON S O. Organosilicon Molecules with Medicinal Applications[J]. Journal of Medicinal Chemistry, 2013, 56(2): 388-405. (b)FUJII S, HASHIMOTO Y. Progress in the Medicinal Chemistry of Silicon: C/Si Exchange and Beyond[J]. Future Medicinal Chemistry, 2017, 9(5): 485-505. (c) RAMESH R, REDDY D S. Quest for Novel Chemical Entities through Incorporation of Silicon in Drug Scaffolds[J]. Journal of Medicinal Chemistry, 2018, 61(9): 3779-3798. (d) DONADEL O J, MARTIN T, MARTIN V S, et al. The Tert-Butyl Dimethyl Silyl Group as an Enhancer of Drug Cytotoxicity Against Human Tumor Cells[J]. Bioorganic Medicinal Chemistry Letter, 2005, 15(15): 3536-3539.
[8] BROOK M A. Silicon in Organic Organometallic, and Polymer Chemistry[M]. 2000.
[9] (a) SHELDRICK W S. Structural Chemistry of Organic Silicon Compounds[J]. Chemistry of Organic Silicon Compounds, 1989, 1: 227-303. (b) RAPPOPORT Z, APELOIG Y, EDITORS. The Chemistry of Organic Silicon Compounds, Volume 2, Part 3[M]. 1998. (c) 汤仁和. 硅手性苯并噻咯的合成研究[D]. 浙江:杭州师范大学,2021.
[10] (a) TACKE R, HEINRICH T. Syntheses of Enantiopure Si-Centrochiral Silicon-based Muscarinic Antagonists Using an Enantioselective Enzymatic Esterification as the Key Step[J]. Silicon Chemistry, 2002, 1(1): 35-39. (b) RENDLER S, AUER G, OESTREICH M. Kinetic Resolution of Chiral Secondary Alcohols by Dehydrogenative Coupling with Recyclable Silicon-Stereogenic Silanes[J]. Angewandte Chemie International Edition, 2005, 44(46): 7620-7624. (c) RENDLER S, AUER G, KELLER M, et al. Preparation of a Privileged Silicon-Stereogenic Silane: Classical Versus Kinetic Resolution[J]. Advanced Synthesis and Catalysis, 2006, 348: 1171-1182. (d) OESTREICH M. Silicon-Stereogenic Silanes in Asymmetric Catalysis[J]. Synlett, 2007(11): 1629-1643. (e) XU L W, LI L, LAI G Q, et al. The Recent Synthesis and Application of Silicon-Stereogenic Silanes: A Renewed and Significant Challenge in Asymmetric Synthesis[J]. Chemical Society Reviews, 2011, 40 (3): 1777-1790. (f) BAUER J O, STROHMANN C. Stereocontrol in Nucleophilic Substitution Reactions at Silicon: The Role of Permutation in Generating Silicon-Centered Chirality[J]. Journal of the American Chemical Society, 2015, 137(13): 4304-4307. (g) BAUER J O, STROHMANN C. Recent Progress in Asymmetric Synthesis and Application of Difunctionalized Silicon-Stereogenic Silanes[J]. European Journal of Inorganic Chemistry, 2016, 2016(18): 2868-2881.
[11] (a) XU LW. Desymmetrization Catalyzed by Transition-Metal Complexes: Enantioselective Formation of Silicon-Stereogenic Silanes[J]. Angewandte Chemie International Edition, 2012, 51(52): 12932-12934. (b) SHINTANI R. Recent Advances in the Transition-Metal-Catalyzed Enantioselective Synthesis of Silicon-Stereogenic Organosilanes[J]. Asian Journal of Organic Chemistry, 2015, 4(6): 510-514. (c) CUI Y M, LIN Y, XU L W. Catalytic Synthesis of Chiral Organoheteroatom Compounds of Silicon, Phosphorus, and Sulfur via Asymmetric Transition Metal-Catalyzed C-H Functionalization[J]. Coordination Chemistry Reviews, 2017, 330: 37-52. (d) WU Y, WANG P. Silicon-Stereogenic Monohydrosilane: Synthesis and Applications[J]. Angewandte Chemie International Edition, 2022, 61(36): e202205382. (e) 刘兴江. 郑州大学. 一种识别谷胱甘肽的荧光探针:CN201910426246.8[P]. 2020-11-24. (f) 刘兴江. 郑州大学. 一种溶酶体靶向的比率型次氯酸荧光探针:CN202110022721.2[P]. 2021-06-11.
[12] (a) LICKISS PD, The Synthesis and Structure of Organosilanols[J]. Advances in Inorganic Chemistry. 1995, 42, 147–262; (b) ZHOU QL, YAN SK, HAN CC, et al. Promising Functional Materials Based on Ladder Polysiloxanes[J]. Advanced Materials. 2008, 20, 2970–2976; (c) JEON M, HAN J, PARK J, Catalytic Synthesis of Silanols from Hydrosilanes and Applications[J]. ACS Catalysis. 2012, 2, 1539–1549.
[13] CHANDRASEKHAR V, BOOMISHANKAR R, NAGENDRAN S. Recent Developments in the Synthesis and Structure of Organosilanols[J]. Chemical Reviews, 2004, 104(12): 5847-5910.
[14] (a) LI L, WEI Y L, XU L W. Organosilicon-Mediated Organic Synthesis (SiMOS): A Personal Account[J]. Synlett, 2020, 31(1): 21-34. (b) NAKAO Y, HIYAMA T. Silicon-based Cross-Coupling Reaction: an Environmentally Benign Version[J]. Chemical Society Reviews, 2011, 40(10): 4893-4901.
[15] (a) DIEMOZ K M, HEIN J E, WILSON S O, et al. Reaction Progress Kinetics Analysis of 1,3-Disiloxanediols as Hydrogen-Bonding Catalysts[J]. Journal of Organic Chemistry, 2017, 82(13): 6738-6747. (b) DIEMOZ K M, WILSON S O, FRANZ A K. Synthesis of Structurally Varied 1,3-Disiloxanediols and Their Activity as Anion-Binding Catalysts[J]. Chemistry - A European Journal, 2016, 22(51): 18349-18353.
[16] PARASRAM M, GEVORGYAN V. Silicon-Tethered Strategies for C-H Functionalization Reactions[J]. Accounts of Chemical Research, 2017, 50(8): 2038-2053.
[17] (a) REMOND E, MARTIN C, MARTINEZ J, et al. Silicon-Containing Amino Acids: Synthetic Aspects, Conformational Studies, and Applications to Bioactive Peptides[J]. Chemical Reviews, 2016, 116(19): 11654-11684. (b) SINGH S, SIEBURTH S M. Serine Protease Inhibition by a Silanediol Peptidomimetic[J]. Organic Letters, 2012, 14(17): 4422-4425. (c) DONADEL O J, MARTIN T, MARTIN V S, et al. The Tert-Butyl Dimethyl Silyl Group as an Enhancer of Drug Cytotoxicity Against Human Tumor Cells[J]. Bioorganic and Medicinal Chemistry Letters, 2005, 15(15): 3536-3539. (d) TACKE R, HANDMANN V I, BERTERMANN R, et al. Sila-Analogues of High-Affinity, Selective σ Ligands of the Spiro[indane-1,4'-piperidine] Type: Syntheses, Structures, and Pharmacological Properties[J]. Organometallics, 2003, 22(5): 916-924.
[18] ZHOU Q, YAN S, HAN C C, et al. Promising Functional Materials based on Ladder Polysiloxanes[J]. Advanced materials, 2008, 20(15): 2970-2976.
[19] (a)KAWAKAMI Y, KAKIHANA Y, OOI O, et al. Control of stereochemical structures of silicon-containing polymeric systems[J]. Polymer International, 2009, 58(3): 279-284. (b)KAMINO B A, BENDER T P. The Use of Siloxanes, Silsesquioxanes, and Silicones in Organic Semiconducting Materials[J]. Chemical Society Reviews, 2013, 42(12): 5119-5130. (c)SUN D, REN Z, BRYCE M R, et al. Arylsilanes and Siloxanes as Optoelectronic Materials for Organic Light-Emitting Diodes (OLEDs)[J]. Journal of Materials Chemistry C, 2015, 3(37): 9496-9508. (d) ZHAI X Y, HU S B, SHI L, et al. Synthesis of Poly(silyl ethers) via Iridium-Catalyzed Dehydrocoupling Polymerization[J]. Organometallics, 2018, 37(14): 2342-2347. (e) WANG X Q, ZHAI X Y, WU B, et al. Synthesis of Chiral Poly(silyl ether)s via CuH-Catalyzed Asymmetric Hydrosilylation Polymerization of Diketones with Silanes[J]. ACS Macro Letters, 2020, 9(7): 969-973.
[20] MERCHANT K J. Potassium Trimethylsilanolate Mediated Hydrolysis of Nitriles to Primary Amides[J]. Tetrahedron Letters, 2000, 41(19): 3747-3749.
[21] HIRABAYASHI K, MORI A, KAWASHIMA J, et al. Palladium-Catalyzed Cross-Coupling of Silanols, Silanediols, and Silanetriols Promoted by Silver(I) Oxide[J]. Journal of Organic Chemistry, 2000, 65(17): 5342-5349.
[22] (a) DENMARK S E, SWEIS R F. Cross-Coupling Reactions of Organosilicon Compounds: New Concepts and Recent Advances[J]. Chemical and Pharmaceutical Bulletin, 2002, 50(12): 1531-1541. (b) DENMARK S E, SWEIS R F. Design and Implementation of New, Silicon-Based, Cross-Coupling Reactions: Importance of Silicon-Oxygen Bonds[J]. Accounts of Chemical Research, 2002, 35(10): 835-846.
[23] WANG C, GE H B. Silanol as a Removable Directing Group for the PdII-Catalyzed Direct Olefination of Arenes[J]. Chemistry – A European Journal, 2011, 17(51): 14371-14374.
[24] KONDO S I, HARADA T, TANAKA R, et al. Anion Recognition by a Silanediol-Based Receptor[J]. Organic Letters, 2006, 8(20): 4621-4624.
[25] TRAN N T, MIN T, FRANZ A K. Silanediol Hydrogen Bonding Activation of Carbonyl Compounds[J]. Chemistry - A European Journal, 2011, 17(36): 9897-9900.
[26] SCHAFER A G, WIETING J M, MATTSON A E. Silanediols: A New Class of Hydrogen Bond Donor Catalysts[J]. Organic Letters, 2011, 13(19): 5228-5231.SHELDRICK W S. Structural Chemistry of Organic Silicon Compounds[J]. Chemistry Organic Silicon Compounds, 1989, 1: 227-303.
[27] JEON M, HAN J, PARK J. Catalytic Synthesis of Silanols from Hydrosilanes and Applications[J]. ACS Catalysis, 2012, 2(8): 1539-1549.
[28] ADAM W, MITCHELL C M, SAHA-MOLLER C R, et al. The Selective Catalytic Oxidation of Silanes to Silanols with H2O2 Activated by the Ti-beta Zeolite[J]. Chemical Communications, 1998(23): 2609-2610.
[29] (a) BARIK C K, GANGULY R, LI Y, et al. Ruthenacyclic Carbamoyl Complexes: Highly Efficient Catalysts for Organosilane Hydrolysis[J]. European Journal of Inorganic Chemistry, 2018, 2018(46): 4982-4986. (b) WANG K K, ZHOU J M, JIANG Y T, et al. Selective Manganese-Catalyzed Oxidation of Hydrosilanes to Silanols under Neutral Reaction Conditions[J]. Angewandte Chemie International Edition, 2019, 58(19): 6380-6384.
[30] (a) CHOI E, LEE C, NA Y, et al. [RuCl2(p-cymene)]2 on Carbon: An Efficient, Selective, Reusable, and Environmentally Versatile Heterogeneous Catalyst[J]. Organic Letters, 2002, 4(14): 2369-2371. (b) MORI K, TANO M, MIZUGAKI T, et al. Efficient Heterogeneous Oxidation of Organosilanes to Silanols Catalyzed by a Hydroxyapatite-Bound Ru Complex in the Presence of Water and Molecular Oxygen[J]. New Journal of Chemistry, 2002, 26(11): 1536-1538. (c) MITSUDOME T, ARITA S, MORI H, et al. Supported Silver-Nanoparticle-Catalyzed Highly Efficient Aqueous Oxidation of Phenylsilanes to Silanols[J]. Angewandte Chemie International Edition, 2008, 47(41): 7938-7940. (d) CHAUHAN B P S, SARKAR A, CHAUHAN M, et al. Water as Green Oxidant: A Highly Selective Conversion of Organosilanes to Silanols with Water[J]. Applied Organometallic Chemistry, 2009, 23(10): 385-390. (e) ASAO N, ISHIKAWA Y, HATAKEYAMA N, et al. Nanostructured Materials as Catalysts: Nanoporous-Gold-Catalyzed Oxidation of Organosilanes with Water[J]. Angewandte Chemie International Edition, 2010, 49(52): 10093-10095. (f) JOHN J, GRAVEL E, HAGEGE A, et al. Catalytic Oxidation of Silanes by Carbon Nanotube-Gold Nanohybrids[J]. Angewandte Chemie International Edition, 2011, 50(33): 7533-7536. (g) SHIMIZU K I, KUBO T, SATSUMA A. Surface Oxygen-Assisted Pd Nanoparticle Catalysis for Selective Oxidation of Silanes to Silanols[J]. Chemistry - A European Journal, 2012, 18(8): 2226-222. (h) KIKUKAWA Y, KURODA Y, YAMAGUCHI K, et al. Diamond-Shaped [Ag4]4+ Cluster Encapsulated by Silicotungstate Ligands: Synthesis and Catalysis of Hydrolytic Oxidation of Silanes[J]. Angewandte Chemie International Edition, 2012, 51(10): 2434-2437. (i) 王红娜. 微弧氧化法制备负载型贵金属催化剂用于高效硅烷氧化[D]. 辽宁:东北大学,2019.
[31] KELLY A T, FRANZ A K. Metal-Free Synthesis of 1,3-Disiloxanediols and Aryl Siloxanols[J]. ACS Omega, 2019, 4(4): 6295-6300.
[32] BAEHR S, BRINKMANN-CHEN S, GARCIA-BORRAS M, et al. Selective Enzymatic Oxidation of Silanes to Silanols[J]. Angewandte Chemie International Edition, 2020, 59(36): 15507-15511.
[33] LIANG H, WANG L J, JI Y X, et al. Selective Electrochemical Hydrolysis of Hydrosilanes to Silanols via Anodically Generated Silyl Cations[J]. Angewandte Chemie International Edition, 2021, 60(4): 1839-1844.
[34] LI J Y, XU D D, SHI G R, et al. Oxidation of Silanes to Silanols with Oxygen via Photoredox Catalysis[J]. ChemistrySelect, 2021, 6(32): 8345-8348.
[35] WANG J, LI B, LIU L C, et al. Metal-Free Visible-Light-Mediated Aerobic Oxidation of Silanes to Silanols[J]. Scientia Sinica Chimica, 2018, 61(12): 1594-1599.
[36] (a) KEITH J M, LARROW J F, JACOBSEN E N. Practical Considerations in Kinetic Resolution Reactions[J]. Advanced Synthesis and Catalysis, 2001, 343(1): 5-26. (b) ROBINSON D E J E, BULL S D. Kinetic Resolution Strategies Using Non-Enzymatic Catalysts[J]. Tetrahedron Asymmetry, 2003, 14(11): 1407-1446. (c) VEDEJS E, JURE M. Efficiency in Nonenzymatic Kinetic Resolution[J]. Angewandte Chemie International Edition, 2005, 44(26): 3974-4001.
[37] YAMAMOTO K, KAWANAMI Y, MIYAZAWA M. Kinetic Resolution of (±)-Cyclohex-1-Enylsilanols by the Sharpless Asymmetric Epoxidation[J]. Journal of the Chemical Society, Chemical Communications, 1993(5): 436-437.
[38] MORI A, TORIYAMA F, KAJIRO H, et al. Synthesis and Optical Resolution of Novel Chiral Silanols[J]. Chemistry Letters, 1999(7): 549-550.
[39] (a) SOMMER L H, ULLAND L A, PARKER G A. Stereochemistry of Asymmetric silicon. XX. Hydroxylation and Carbene Insertion Reactions of R3SiH[J]. Journal of the American Chemical Society, 1972, 94(10): 3469-3471. (b) ADAM W, MELLO R, CURCI R. O-Atom Insertion into Si-H Bonds by Dioxiranes: A Stereospecific and Direct Conversion of Silanes into Silanols[J]. Angewandte Chemie International Edition, 1990, 29(8): 890-891.(c) CAVICCHIOLI M, MONTANARI V, RESNATI G. Oxyfunctionalization Reactions by Perfluoro cis-2,3-Dialkyloxaziridines. Enantioselective Conversion of Silanes into Silanols[J]. Tetrahedron Letters, 1994, 35(34): 6329-6330. (d) ADAM W, MITCHELL C M, SAHA-MOELLER C R, et al. Host-Guest Chemistry in a Urea Matrix: Catalytic and Selective Oxidation of Triorganosilanes to the Corresponding Silanols by Methyltrioxorhenium and the Urea/Hydrogen Peroxide Adduct[J]. Journal of the American Chemical Society, 1999, 121(10): 2097-2103. (e)LEE M, KO S, CHANG S. Highly Selective and Practical Hydrolytic Oxidation of Organosilanes to Silanols Catalyzed by a Ruthenium Complex[J]. Journal of the American Chemical Society, 2000, 122(48): 12011-12012. (f) ISHIMOTO R, KAMATA K, MIZUNO N. Highly Selective Oxidation of Organosilanes to Silanols with Hydrogen Peroxide Catalyzed by a Lacunary Polyoxotungstate[J]. Angewandte Chemie International Edition, 2009, 48(47): 8900-8904. (g) OKADA Y, OBA M, ARAI A, et al. Diorganotelluride-Catalyzed Oxidation of Silanes to Silanols under Atmospheric Oxygen[J]. Inorganic Chemistry, 2010, 49(2): 383-385. (h) SOMMER L H, ROSBOROUGH K T. Stereochemistry of Asymmetric Silicon. XVII. Synthesis, Resolution, and Stereochemistry of the 1,2,2,2-Tetraphenyl-1-Methyldisilane System[J]. Journal of the American Chemical Society, 1969, 91(25): 7067-7076. (i) KAMACHI T, SHIMIZU K I, YOSHIHIRO D, et al. Oxidation of Silanes to Silanols on Pd Nanoparticles: H2 Desorption Accelerated by Surface Oxygen Atom[J]. Journal of Physical Chemistry C, 2013, 117(44): 22967-22973.
[40] TOMOOKA K, NAKAZAKI A, NAKAI T. A Novel Aryl Migration from Silicon to Carbon: An Efficient Approach to Asymmetric Synthesis of α-Aryl β-Hydroxy Cyclic Amines and Silanols[J]. Journal of the American Chemical Society, 2000, 122(2): 408-409.
[41] IGAWA K, TAKADA J, SHIMONO T, et al. Enantioselective Synthesis of Silanol[J]. Journal of the American Chemical Society, 2008, 130(48): 16132-16133.
[42] IGAWA K, YOSHIHIRO D, ICHIKAWA N, et al. Catalytic Enantioselective Synthesis of Alkenylhydrosilane[J]. Angewandte Chemie International Edition, 2012, 51(51): 12745-12748.
[43] BI X F, FENG J, XUE X P, et al. Construction of Axial Chirality and Silicon-Stereogenic Center via Rh-Catalyzed Asymmetric Ring-Opening of Silafluorenes[J]. Organic Letters, 2021, 23(8): 3201-3206.
[44] ZHANG H P, ZHAO D B. Synthesis of Silicon-Stereogenic Silanols Involving Iridium-Catalyzed Enantioselective C-H Silylation Leading to a New Ligand Scaffold[J]. ACS Catalysis, 2021, 11(17): 10748-10753.
[45] SHINTANI R. Recent Progress in Catalytic Enantioselective Desymmetrization of Prochiral Organosilanes for the Synthesis of Silicon-Stereogenic Compounds[J]. Synlett, 2018, 29(4): 388-396.
[46] (a) CORRIU R J P, MOREAU J J E. Asymmetric Synthesis of Alkoxysilanes Catalyzed by Rhodium Complexes[J]. Tetrahedron Letters, 1973(45): 4469-4472. (b) HAYASHI T, YAMAMOTO K, KUMADA M. Asymmetric Synthesis of Bifunctional Organosilicon Compounds by Hydrosilylation[J]. Tetrahedron Letters, 1974(4): 331-334.
[47] OHTA T, ITO M, TSUNETO A, et al. Asymmetric Synthesis of Silanes with a Stereogenic Center at Silicon via Hydrosilylation of Symmetric Ketones with Prochiral Diaryl Silanes Catalyzed by Binap-RhI Complexes[J]. Journal of the Chemical Society, Chemical Communications, 1994(21): 2525-2526.
[48] TAMAO K, NAKAMURA K, ISHII H, et al. Axially Chiral Spirosilanes via Catalytic Asymmetric Intramolecular Hydrosilation[J]. Journal of the American Chemical Society, 1996, 118(49): 12469-12470.
[49] WEN H N, WAN X L, HUANG Z. Asymmetric Synthesis of Silicon-Stereogenic Vinylhydrosilanes by Cobalt-Catalyzed Regio- and Enantioselective Alkyne Hydrosilylation with Dihydrosilanes[J]. Angewandte Chemie International Edition, 2018, 57(21): 6319-6323.
[50] YE F, XU Z, XU L W. The Discovery of Multifunctional Chiral P Ligands for the Catalytic Construction of Quaternary Carbon/Silicon and Multiple Stereogenic Centers[J]. Accounts of Chemical Research, 2021, 54(2): 452-470.
[51] ZHAN G, TENG H L, LUO Y, et al. Enantioselective Construction of Silicon-Stereogenic Silanes by Scandium-Catalyzed Intermolecular Alkene Hydrosilylation[J]. Angewandte Chemie International Edition, 2018, 57(38): 12342-12346.
[52] HE T, LIU L C, MA W P, et al. Enantioselective Construction of Si-Stereogenic Center via Rhodium-Catalyzed Intermolecular Hydrosilylation of Alkene[J]. Chemistry - A European Journal, 2020, 26(71): 17011-17015.
[53] ZHENG L, NIE X X, WU Y, et al. Construction of Si-Stereogenic Silanes through C-H Activation Approach[J]. European Journal of Organic Chemistry, 2021, 2021(44): 6006-6014.
[54] YASUTOMI Y, SUEMATSU H, KATSUKI T. Iridium(III)-Catalyzed Enantioselective Si-H Bond Insertion and Formation of an Enantioenriched Silicon Center[J]. Journal of the American Chemical Society, 2010, 132(13): 4510-4511.
[55] JAGANNATHAN J R, FETTINGER J C, SHAW J T, et al. Enantioselective Si-H Insertion Reactions of Diarylcarbenes for the Synthesis of Silicon-Stereogenic Silanes[J]. Journal of the American Chemical Society, 2020, 142(27): 11674-11679.
[56] KURIHARA Y, NISHIKAWA M, YAMANOI Y, et al. Synthesis of Optically Active Tertiary Silanes via Pd-Catalyzed Enantioselective Arylation of Secondary Silanes[J]. Chemical Communications, 2012, 48(94): 11564-11566.
[57] CHEN L, HUANG J B, XU Z, et al. Palladium-Catalyzed Si-C Bond-Forming Silylation of Aryl Iodides with Hydrosilanes: an Enhanced Enantioselective Synthesis of Silicon-Stereogenic Silanes by Desymmetrization[J]. RSC Advances, 2016, 6(71): 67113-67117.
[58] KUNINOBU Y, YAMAUCHI K, TAMURA N, et al. Rhodium-Catalyzed Asymmetric Synthesis of Spirosilabifluorene Derivatives[J]. Angewandte Chemie International Edition, 2013, 52(5): 1520-1522.
[59] MURAI M, TAKEUCHI Y, YAMAUCHI K, et al. Rhodium-Catalyzed Synthesis of Chiral Spiro-9-silabifluorenes by Dehydrogenative Silylation: Mechanistic Insights into the Construction of Tetraorganosilicon Stereocenters[J]. Chemistry - A European Journal, 2016, 22(17): 6048-6058.
[60] MU D L, YUAN W, CHEN S Y, et al. Streamlined Construction of Silicon-Stereogenic Silanes by Tandem Enantioselective C-H Silylation/Alkene Hydrosilylation[J]. Journal of the American Chemical Society, 2020, 142(31): 13459-13468.
[61] MA W P, LIU L C, AN K, et al. Rhodium-Catalyzed Synthesis of Chiral Monohydrosilanes by Intramolecular C-H Functionalization of Dihydrosilanes[J]. Angewandte Chemie International Edition, 2021, 60(8): 4245-4251.
[62] YUAN W, YOU L J, LIN W D, et al. Asymmetric Synthesis of Silicon-Stereogenic Monohydrosilanes by Dehydrogenative C-H Silylation[J]. Organic Letters, 2021, 23(4): 1367-1372.
[63] CHEN S Y, MU D L, MAI P L, et al. Enantioselective Construction of Six- and Seven-membered Triorgano-Substituted Silicon-Stereogenic Heterocycles[J]. Nature Communications, 2021, 12(1): 1249.
[64] CHEN S Y, ZHU J F, KE J, et al. Enantioselective Intermolecular C-H Silylation of Heteroarenes for the Synthesis of Acyclic Si-Stereogenic Silanes[J]. Angewandte Chemie International Edition, 2022, 61(21): e202117820.
[65] YANG B, YANG W, GUO Y H, et al. Enantioselective Silylation of Aliphatic C-H Bonds for the Synthesis of Silicon-Stereogenic Dihydrobenzosiloles[J]. Angewandte Chemie International Edition, 2020, 59(49): 22217-22222.
[66] GUO Y H, LIU M M, ZHU X J, et al. Catalytic Asymmetric Synthesis of Silicon-Stereogenic Dihydrodibenzosilines: Silicon Central-to-Axial Chirality Relay[J]. Angewandte Chemie International Edition, 2021, 60(25): 13887-13891.
[67] ZHU J F, CHEN S Y, HE C. Catalytic Enantioselective Dehydrogenative Si-O Coupling to Access Chiroptical Silicon-Stereogenic Siloxanes and Alkoxysilanes[J]. Journal of the American Chemical Society, 2021, 143(14): 5301-5307.
[68] ZHANG L X, AN K, WANG Y, et al. A Combined Computational and Experimental Study of Rh-Catalyzed C-H Silylation with Silacyclobutanes: Insights Leading to a More Efficient Catalyst System[J]. Journal of the American Chemical Society, 2021, 143(9): 3571-3582.