硅手性一氢硅烷和聚合物的合成及其应用探索

手性是自然界的基本属性之一，生命物质如蛋白质、核酸、多糖等都是手性的。含碳手性的有机小分子及高分子化合物在生命医药、功能材料和化学合成领域有着广泛的应用。而Si是C的生物电子等排体，因此，研究硅手性分子的高效合成及功能具有重要的理论意义和应用价值。硅手性硅烷已被报道作为手性助剂应用于有机合成中，其中，一氢硅烷（R1R2R3–SiH）由于其含有一个Si–H键能进行立体专一性转化而占有重要地位。本论文主要围绕硅手性一氢硅烷和聚合物的合成策略及分子功能的开发展开了深入研究，成功利用铑催化二氢硅烷（R1R2–SiH2）的分子间Si–H/X–H（X = C, O）不对称脱氢偶联反应，高效、高对映选择性地实现了系列新型硅手性一氢硅烷和聚合物的构建。主要内容如下：

发展了铑催化二氢硅烷与硅醇、醇的分子间不对称Si–H/O–H脱氢偶联反应，实现了系列新型硅手性一氢硅氧烷和硅醚的高效、高对映选择性构建（高达99% ee）。反应体系具有很好的底物普适性和官能团兼容性，各种吸电子、供电子、杂环取代的二氢硅烷，各种芳基、烷基、以及含生物活性分子、药物分子核心骨架的醇类都能兼容。机理研究表明，二氢硅烷对Rh−H的氧化加成和随后的脱H2步骤为可逆过程，R–OH与Rh−Si中间体的σ-复分解过程涉及反应的决速步骤。此外，对硅手性硅醚的光物理化学性质进行测试发现，含π-共轭芘单元取代的硅手性硅醚分子III-6a~III-6c在365 nm紫外光源照射下展现出蓝、绿光，具有CPL活性。其中III-6c的发光不对称因子（glum）高达0.011，同时具有0.55的荧光量子产率（ΦF）。通过将硅手性硅醚III-6a与其碳手性类似物III-6a'的CPL活性测试结果进行对比发现，含硅手性硅醚（III-6a）的发光不对称因子和荧光量子产率均显著高于其碳手性类似物III-6a'。

发展了铑催化二氢硅烷与杂芳烃的分子间不对称Si–H/C–H脱氢偶联反应，实现了系列新型单、双硅手性杂芳基一氢硅烷的高效、高对映选择性构建（高达99% ee）。其中，所得的双硅手性杂芳基一氢硅烷可作为聚合单体，与含硅双烯在Karstedt催化剂条件下反应，以中等的数均分子量合成以硅手性杂芳基硅烷作为主链的手性聚合物。

发展了铑催化双二氢硅烷与二醇的分子间不对称Si–H/O–H脱氢偶联聚合反应，实现了系列新型硅手性一氢聚硅醚和聚碳硅氧烷（高达99% ee）的高效、高对映选择性构建。与常见的甲基、苯基取代的聚硅醚不同的是，选用大位阻如叔丁基、环己基取代的二氢硅烷作为聚合单体：1）使所得产物具有更高的热稳定性；2）确保反应获得高对映选择性；3）有效抑制产物中剩余的Si–H键进一步发生副反应。硅手性聚硅醚的圆二色谱测试结果表明，聚硅醚的手性是由手性铑催化剂诱导的硅原子中心的不对称性决定的。此外，所得的硅手性一氢聚硅醚可在一定条件下与醇类、烯烃进行立体专一性的后修饰反应，得到相应的四取代硅手性聚硅醚。

[1] TRéGUER 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.
[2] STRUYF E, SMIS A, VAN DAMME S, et al. The Global Biogeochemical Silicon Cycle[J]. Silicon, 2009, 1(4): 207-213.
[3] MEANWELL N A. Synopsis of Some Recent Tactical Application of Bioisosteres in Drug Design[J]. Journal of Medicinal Chemistry, 2011, 54(8): 2529-2591.
[4] THOMAS M J K. Silicon in Organic, Organometallic and Polymer Chemistry[M]. Michael A Brook. John Wiley & Sons, New York, 2000.
[5] RAPPOPORT Z, APELOIG Y, Eds. The Chemistry of Organic Silicon Compounds[M]. Wiley, Chichester, 2003.
[6] HIYAMA T, OESTREICH M, Eds. Organosilicon Chemistry: Novel Approaches and Reactions[M]. Wiley: Weinheim, Germany, 2019.
[7] WEICKGENANNT A， OESTREICH M. The Renaissance of Silicon Stereogenic Silanes: A Personal Account[M]. Asymmetric Synth. II 2013, 35−42.
[8] SOMMER L H. Stereochemistry, Mechanism and Silicon; An Introduction to the Dynamic Stereochemistry and Reaction Mechanisms of Silicon Centers [M]. McGraw-Hill Series in Advanced Chemistry; McGrawHill: New York, 1965
[9] OESTREICH M. Silicon-Stereogenic Silanes in Asymmetric Catalysis[J]. Synlett, 2007, 2007(11): 1629-1643.
[10] 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.
[11] RENDLER S, AUER G, KELLER M, et al. Preparation of a Privileged Silicon-Stereogenic Silane: Classical Versus Kinetic Resolution[J]. Advanced Synthesis & Catalysis, 2006, 348(10-11): 1171-1182.
[12] 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.
[13] LUCAS P, ROBIN J-J. Silicone-Based Polymer Blends: An Overview of The Materials and Processes[J]. Advances in Polymer Science, 2007, 209 (Functional Materials and Biomaterials): 111-147.
[14] 冯圣玉，张洁，利美江，等. 有机硅高分子及其应用［M］. 北京：化学工业出版社，2004.
[15] 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.
[16] WU Y, WANG P. Silicon-Stereogenic Monohydrosilane: Synthesis and Applications[J]. Angewandte Chemie International Edition, 2022, 61(36): e202205382.
[17] YUAN W, HE C. Enantioselective C–H Functionalization toward Silicon-Stereogenic Silanes[J]. Synthesis, 2022, 54(08): 1939-1950.
[18] GE Y, HUANG X, KE J, et al. Transitionmetal-Catalyzed Enantioselective C−H Silylation [J]. Chem Catalysis, 2022, 2(11): 2898-928.
[19] SOMMER L H, FRYE C L. Optically Acttive Organosilicon Compounds Having Reactive Groups Bonded to Asymmetric Silicon. Displacement Reactions at Silicon with Pure Retention and Pure Invevtion of Configuration[J]. Journal of the American Chemical Society, 1959, 81(4): 1013.
[20] SOMMER L H, FRYE C L, PARKER G A, et al. Stereochemistry of Asymmetric Silicon. I. Relative and Absolute Configurations of Optically Active α-Naphthylphenylmethylsilanes[J]. Journal of the American Chemical Society, 1964, 86(16): 3271-3276.
[21] 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.
[22] CORRIU R, MASSE J. Stereochemistry and Mechanism of Nucleophilic Substitution Silicon Atoms. An Asymmetric Cyclosilane[J]. Bulletin de la Société Chimique de France, 1969, (10): 3491-3496.
[23] CORRIU R J P, OULD-KADA S, LANNEAU G. Methylphenyl- triphenylgermylsilanes Fonctionnels Optiquement Actifs: I. Synthese et Stereochimie[J]. Journal of Organometallic Chemistry, 1983, 248(1): 23-37.
[24] DAIYO T, KATSUTOSHI M, MASANORI K, et al. Optical Resolutions and Configurations of Benzylmethylphenylsilylmethylamine and Its Derivatives[J]. Bulletin of the Chemical Society of Japan, 1980, 53(3): 789-794.
[25] JANKOWSKI P, SCHAUMANN E, WICHA J, et al. Facile Synthesis of Enantiomerically Pure Tert-butyl(methyl)phenylsilanes[J]. Tetrahedron: Asymmetry, 1999, 10(3): 519-526.
[26] JANKOWSKI P, SCHAUMANN E, WICHA J, et al. Preparation of Optically Active n-Butyl(methyl)phenyl-, tert-Butyl(methyl)phenyl- and iso-Propyl-(methyl)phenylsilanes from the Corresponding Silyl Chlorides Using 2,2′-dihydroxy-1,1′-binaphthyls as Resolving Agents[J]. Chemical Communications, 2000, (12): 1029-1030.
[27] TRZOSS M, SHAO J, BIENZ S. Preparation of a Si-Centered Chiral Auxiliary by Resolution[J]. Tetrahedron: Asymmetry, 2004, 15(9): 1501-1505.
[28] KIMIKO K, TAKAYUKI K, SHINJI M. Asymmetric Synthesis of Silicon Compounds Using Chiral 5,6-Dimethoxy-1,3,2-dioxasilacycloheptane Derivatives[J]. Chemistry Letters, 1987, 16(1): 101-104.
[29] OKA N, NAKAMURA M, SOEDA N, et al. Stereocontrolled Synthesis of Tertiary Silanes via Optically Pure 1,3,2-Oxazasilolidine Derivatives[J]. Journal of Organometallic Chemistry, 2009, 694(14): 2171-2178.
[30] CORRIU R J P, MOREAU J J E. Asymmetric Synthesis at Silicon: II. Alcoholysis of Prochiral Organosilicon Compounds Catalysed by Rhodium Complexes[J]. Journal of Organometallic Chemistry, 1976, 120(3): 337-346.
[31] GUO J, WANG H, XING S, et al. Cobalt-Catalyzed Asymmetric Synthesis of gem-Bis(silyl)alkanes by Double Hydrosilylation of Aliphatic Terminal Alkynes[J]. Chem, 2019, 5(4): 881-895.
[32] CORRIU R J P, MOREAU J J E. Asymmetric Hydrosilylation of Ketones Catalysed by a Chiral Rhodium Complex[J]. Journal of Organometallic Chemistry, 1974, 64(3): C51-C4.
[33] Hayashi T, Yamamoto K, Kumada M. Asymmetric Synthesis of Bifunctional Organosilicon Compounds via Hydrosilylation[J]. Tetrahedron Letters, 1974, 15(4): 331-334.
[34] HAYASHI T, YAMAMOTO K, KUMADA M, et al. Asymmetric Synthesis of Silanes with a Stereogenic Centre at Silicon via Hydrosilylation of Symmetric Ketones with Prochiral Diaryl Silanes Catalysed by Binap–Rh Complexes[J]. Journal of the Chemical Society, Chemical Communications, 1994, (21): 2525-2526.
[35] 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.
[36] IGAWA K, YOSHIHIRO D, ICHIKAWA N, et al. Catalytic Enantioselective Synthesis of Alkenylhydrosilanes[J]. Angewandte Chemie International Edition, 2012, 51(51): 12745-12748.
[37] WEN H, WAN X, 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.
[38] XIE J-L, XU Z, ZHOU H-Q, et al. Palladium-Catalyzed Hydrosilylation of Ynones to Access Silicon-Stereogenic Silylenones by Stereospecific Aromatic Interaction-Assisted Si−H Activation[J]. Science China Chemistry, 2021, 64(5): 761-769.
[39] 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.
[40] 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.
[41] HUANG Y-H, WU Y, ZHU Z, et al. Enantioselective Synthesis of Silicon-Stereogenic Monohydrosilanes by Rhodium-Catalyzed Intramolecular Hydrosilylation[J]. Angewandte Chemie International Edition, 2022, 61(1): e202113052.
[42] LU W, ZHAO Y, MENG F. Cobalt-Catalyzed Sequential Site- and Stereoselective Hydrosilylation of 1,3- and 1,4-Enynes[J]. Journal of the American Chemical Society, 2022, 144(12): 5233-5240.
[43] 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.
[44] NAKAGAWA Y, CHANTHAMATH S, FUJISAWA I, et al. Ru(ii)-Pheox-Catalyzed Si–H Insertion Reaction: Construction of Enantioenriched Carbon and Silicon Centers[J]. Chemical Communications, 2017, 53(26): 3753-3756.
[45] 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.
[46] 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.
[47] 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.
[48] MU D, YUAN W, CHEN S, 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.
[49] YUAN W, YOU L, LIN W, et al. Asymmetric Synthesis of Silicon-Stereogenic Monohydrosilanes by Dehydrogenative C–H Silylation[J]. Organic Letters, 2021, 23(4): 1367-1372.
[50] MA W, 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.
[51] CHEN S, MU D, MAI P-L, et al. Enantioselective Construction of Six- and Seven-Membered Triorgano-Substituted Silicon-Stereogenic Heterocycles [J]. Nature Communications, 2021, 12(1): 1249.
[52] GUO Y, LIU M-M, ZHU X, 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.
[53] CORRIU R J P, MOREAU J J E. Synthese Asymetrique D'alcoxysilanes Catalysee par des Complexes du Rhodium[J]. Tetrahedron Letters, 1973, 14(45): 4469-4472.
[54] SCHMIDT D R, O'MALLE S J, LEIGHTON J L, Leighton J L. Catalytic Asymmetric Silane Alcoholysis:  Practical Access to Chiral Silanes[J]. Journal of the American Chemical Society, 2003, 125(5): 1190-1191.
[55] LI Y, SEINO M, KAWAKAMI Y. Asymmetric Synthesis of Optically Active Poly(silyl ether)s Having Reactive Si−H Groups by Stereoselective Cross-Dehydrocoupling Polymerization of Bis(silane)s with Diols[J]. Macromolecules, 2000, 33(15): 5311-5314.
[56] ZHAI X-Y, WANG X-Q, ZHOU Y-G. Cobalt-Catalyzed Selective Dehydrocoupling Polymerization of Prochiral Silanes and Diols[J]. European Polymer Journal, 2020, 134: 109832.
[57] XU J-X, CHEN M-Y, ZHENG Z-J, et al. Platinum-Catalyzed Multicomponent Alcoholysis/Hydrosilylation and Bis-hydrosilylation of Alkynes with Dihydrosilanes[J]. ChemCatChem, 2017, 9(16): 3111-3116.
[58] LONG P-W, BAI X-F, YE F, et al. Construction of Six-Membered Silacyclic Skeletons via Platinum-Catalyzed Tandem Hydrosilylation/Cyclization with Dihydrosilanes[J]. Advanced Synthesis & Catalysis, 2018, 360(15): 2825-2830.
[59] YUAN W, ZHU X, XU Y, et al. Synthesis of Si-stereogenic Silanols by Catalytic Asymmetric Hydrolytic Oxidation[J]. Angewandte Chemie International Edition, 2022, 61(31): e202204912.
[60] GAO J, MAI P-L, GE Y, et al. Copper-Catalyzed Desymmetrization of Prochiral Silanediols to Silicon-Stereogenic Silanols[J]. ACS Catalysis, 2022, 12(14): 8476-8483.
[61] MURATA M, SUZUKI K, WATANABE S, et al. Synthesis of Arylsilanes via Palladium(0)-Catalyzed Silylation of Aryl Halides with Hydrosilane[J]. The Journal of Organic Chemistry, 1997, 62(24): 8569-8571.
[62] YAMANOI Y, TAIRA T, SATO J-I, et al. Efficient Preparation of Monohydrosilanes Using Palladium-catalyzed Si−C Bond Formation[J]. Organic Letters, 2007, 9(22): 4543-4546.
[63] 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.
[64] 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.
[65] LU X, LI L, YANG W, et al. Catalytic Synthesis of Functional Silicon-Stereogenic Silanes through Candida Antarctica Lipase B Catalyzed Remote Desymmetrization of Silicon-Centered Diols[J]. European Journal of Organic Chemistry, 2013, 2013(26): 5814-5819.
[66] AN K, MA W, LIU L-C, et al. Rhodium Hydride Enabled Enantioselective Intermolecular C–H Silylation to Access Acyclic Stereogenic Si–H[J]. Nature Communications, 2022, 13(1): 847.
[67] SOMMER L H, KORTE W D. Stereochemistry of Asymmetric Silicon. VIII. Stereochemistry Crossover and Leaving Group Basicity in Organometallic Coupling Reactions[J]. Journal of the American Chemical Society, 1967, 89(23): 5802-5806.
[68] SOMMER L H, ULLAND L A, RITTER A. Dihalocarbene Insertions into Optically Active R3Si*H with Retention of Configuration[J]. Journal of the American Chemical Society, 1968, 90(16): 4486.
[69] BROOK A G, DUFF J M, ANDERSON D G. Optically Active Silyl- and Germylmethyllithium Reagents and the Stereochemistry of Carbene Insertions into the Silicon-Hydrogen and Germanium-Hydrogen Bonds[J]. Journal of the American Chemical Society, 1970, 92(26): 7567-7572.
[70] STANG P J, LEARNED A E. Stereochemistry and Mode of Intermolecular Silicon-Hydrogen Unsaturated Carbene Insertions[J]. Journal of the American Chemical Society, 1987, 109(16): 5019-5020.
[71] STANG P J, LEARNED A E. Axial Chirality by Asymmetric Induction. Diastereomeric Allene Formation via Silicon as a Chiral Auxiliary[J]. The Journal of Organic Chemistry, 1989, 54(8): 1779-1781.
[72] SOMMER L H, MICHAEL K W, FUJIMOTO H. Stereochemistry of Asymmetric Silicon. Stereospecific Platinum-Catalyzed Hydrosilation of 1-Octene with Optically Active R3Si*H[J]. Journal of the American Chemical Society, 1967, 89(6): 1519-1521.
[73] BROOK A G, PANNELL K H, ANDERSON D G. Alpha.-Silyl-cis-Stilbenes from Silylcarbonium Ions and from the Platinum-Catalyzed Addition of Silanes to Diphenylacetylene[J]. Journal of the American Chemical Society, 1968, 90(16): 4374-4377.
[74] SOMMER L H, LYONS J E. Stereospecific Substitution Reactions of Optically Active R3Si*H Catalyzed by Palladium and Nickel[J]. Journal of the American Chemical Society, 1967, 89(6): 1521-1522.
[75] SOMMER L H, LYONS J E. The Stereochemistry of the Silicon-Cobalt Bond and some Implications for Homogeneous Transition-Metal Catalysis[J]. Journal of the American Chemical Society, 1968, 90(15): 4197-4199.
[76] SOMMER L H, LYONS J E. The Stereochemistry of the Silicon-Cobalt Bond and Some Implications for Homogeneous Transition-Metal Catalysis[J]. Journal of the American Chemical Society, 1968, 90(15): 4197-4199.
[77] EABORN C, KAPOOR P N, TUNE D J, et al. The Preparation of Optically Active Germyl- and Silylplatinum Complexes[J]. Journal of Organometallic Chemistry, 1972, 34(1): 153-154.
[78] EABORN C, TUNE D J, WALTON D R M. Stereochemistry of the Formation and Cleavage of Silicon–Platinum Bonds[J]. Journal of the Chemical Society, Dalton Transactions, 1973, (21): 2255-2264.
[79] JOHANNSEN M, JøRGENSEN K A, HELMCHEN G, Helmchen G. Synthesis and Application of the First Chiral and Highly Lewis Acidic Silyl Cationic Catalyst[J]. Journal of the American Chemical Society, 1998, 120(30): 7637-7638.
[80] IGAWA K, KOKAN N, TOMOOKA K. Asymmetric Synthesis of Chiral Silacarboxylic Acids and Their Ester Derivatives[J]. Angewandte Chemie International Edition, 2010, 49(4): 728-731.
[81] KAWAKAMI Y, TAKAHASHI T, YADA Y, et al. Elucidation of the Stereochemical Pathway to Isotactic Poly[(methylphenylsilylene)- trimethylene] from Allylmethylphenylsilane[J]. Polymer Journal, 1998, 30(12): 1001-1003.
[82] KAWAKAMI Y, TAKEYAMA K, KOMURO K, et al. Synthesis of Poly(methylphenylsilylenetrimethylene) Rich in Isotacticity Characterized by 750 MHz 1H NMR[J]. Macromolecules, 1998, 31(2): 551-553.
[83] KAWAKAMI Y, NAKAO K, SHINKE S, et al. Synthesis and Polyaddition Reaction of Optically Active Methylphenylpropargylsilane[J]. Macromolecules, 1999, 32(20): 6874-6876.
[84] FRY J L. Stereoselective Attack at on Enantiotopic Face of a Carbonium Ion by Chiral Nucleophile[J]. Journal of the American Chemical Society, 1971, 93(14): 3558-3559.
[85] FRY J L, ADLINGTON M G. Asymmetric Reductions of Carbocations by Chiral Organosilicon Hydrides. The Stereochemical Nature of the Carbocation Captured[J]. Journal of the American Chemical Society, 1978, 100(24): 7641-7644.
[86] JUNG M E, HOGAN K T. Chirality Transfer from Silicon to Carbon: Use of Optically Pure Cyclic Silanes with a Binaphthalene Chiral Unit[J]. Tetrahedron Letters, 1988, 29(48): 6199-6202.
[87] OESTREICH M. Chirality Transfer from Silicon to Carbon[J]. Chemistry – A European Journal, 2006, 12(1): 30-37.
[88] OESTREICH M, RENDLER S. “True” Chirality Transfer from Silicon to Carbon: Asymmetric Amplification in a Reagent-Controlled Palladium-Catalyzed Hydrosilylation[J]. Angewandte Chemie International Edition, 2005, 44(11): 1661-1664.
[89] RENDLER S, OESTREICH M, BUTTS C P. et al. Intermolecular Chirality Transfer from Silicon to Carbon:  Interrogation of the Two-Silicon Cycle for Pd-Catalyzed Hydrosilylation by Stereoisotopochemical Crossover[J]. Journal of the American Chemical Society, 2007, 129(3): 502-503.
[90] 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.
[91] KLARE H F T, OESTREICH M. Chiral Recognition with Silicon-Stereogenic Silanes: Remarkable Selectivity Factors in the Kinetic Resolution of Donor-Functionalized Alcohols[J]. Angewandte Chemie International Edition, 2007, 46(48): 9335-9338.
[92] STEVES A, OESTREICH M. Facile Preparation of CF3-Substituted Carbinols with an Azine Donor and Subsequent Kinetic Resolution Through Stereoselective Si–O Coupling[J]. Organic & Biomolecular Chemistry, 2009, 7(21): 4464-4469.
[93] RENDLER S, PLEFKA O, KARATAS B, et al. Stereoselective Alcohol Silylation by Dehydrogenative Si–O Coupling: Scope, Limitations, and Mechanism of the Cu–H-Catalyzed Non-Enzymatic Kinetic Resolution with Silicon-Stereogenic Silanes[J]. Chemistry – A European Journal, 2008, 14(36): 11512-11528.
[94] RENDLER S, OESTREICH M. Conclusive Evidence for an SN2-Si Mechanism in the B(C6F5)3-Catalyzed Hydrosilylation of Carbonyl Compounds: Implications for the Related Hydrogenation[J]. Angewandte Chemie International Edition, 2008, 47(32): 5997-6000.
[95] CORRIU R, MASSE J. Reactions Stereospecifiques de lithiens sur un Bicyclosilane Asymetrique[J]. Tetrahedron Letters, 1968, 9(50): 5197-5200.
[96] ROARK D N, SOMMER L H. Dramatic Stereochemistry Crossover to Retention of Configuration with Angle-Strained Asymmetric Silicon[J]. Journal of the American Chemical Society, 1973, 95(3): 969-971.
[97] BROOK A G, WARNER C M. The Stereospecific Synthesis and Rearrangement of an α-Hydroxysilane[J]. Tetrahedron Letters, 1962, 3(18): 815-819.
[98] BROOK A G, LIMBURG W W. Stereochemistry of α-Silylcarbinol Rearrangements. II. The Absolute Configuration of Asymmetric Silanes[J]. Journal of the American Chemical Society, 1963, 85(6): 832-833.
[99] SOMMER L H, CITRON J D. Group VIII Metal-Catalyzed Reactions of Organosilicon Hydrides with Amines, Hydrogen Halides, and Hydrogen Sulfide[J]. The Journal of Organic Chemistry, 1967, 32(8): 2470-2472.
[100] SOMMER L H, ULLAND L A, PARKER G A. Stereochemistry of Asymmetric Silicon. Hydroxylation and Carbene Insertion Reactions of R3SiH[J]. Journal of the American Chemical Society, 1972, 94(10): 3469-3471.
[101] SOMMER L H, ULLAND L A, RITTER A. Dihalocarbene Insertions into Optically Active R3Si*H with Retention of Configuration[J]. Journal of the American Chemical Society, 1968, 90(16): 4486.
[102] METSäNEN T T, HROBáRIK P, KLARE H F T, et al. Insight into the Mechanism of Carbonyl Hydrosilylation Catalyzed by Brookhart’s Cationic Iridium(III) Pincer Complex[J]. Journal of the American Chemical Society, 2014, 136(19): 6912-6915.
[103] IGLESIAS M, FERNáNDEZ-ALVAREZ F J, ORO L A. Outer-Sphere Ionic Hydrosilylation Catalysis[J]. ChemCatChem, 2014, 6(9): 2486-2489.
[104] KOGA S, UEKI S, SHIMADA M, et al. Access to Chiral Silicon Centers for Application to Circularly Polarized Luminescence Materials[J]. The Journal of Organic Chemistry, 2017, 82(12): 6108-6117.
[105] FRISCH M J, TRUCKS G W, SCHLEGEL H B, et al. Gaussian 16, Revision A.03[CP]. Gaussian, Inc.: Wallingford, CT, 2016.
[106] BECKE A D. Density-Functional Thermochemistry. III. The Role of Exact Exchange[J]. The Journal of Chemical Physics, 1993, 98(7): 5648-5652.
[107] LEE C, YANG W, PARR R G. Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron Density[J]. Physical Review B, 1988, 37(2): 785-789.
[108] ZHAO Y, TRUHLAR D G. The M06 Suite of Density Functionals for Main Group Thermochemistry, Thermochemical Kinetics, Noncovalent Interactions, Excited states, and Transition Elements: Two New Functionals and Systematic Testing of Four M06-Class Functionals and 12 other Functionals[J]. Theoretical Chemistry Accounts, 2008, 120(1): 215-241.
[109] MARENICH A V, CRAMER C J, TRUHLAR D G. Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions[J]. The Journal of Physical Chemistry B, 2009, 113(18): 6378-6396.
[110] LEGAULT C Y. CYLView, 1.0b; Universitéde Sherbrooke: Québec, Montreal, Canada, 2009; http://www.cylview.org.
[111] LALONDE M, CHAN T H. Use of Organosilicon Reagents as Protective Groups in Organic Synthesis[J]. Synthesis, 1985, 1985(09): 817-845.
[112] CHAN T H, WANG D. Chiral Organosilicon Compounds in Asymmetric Synthesis[J]. Chemical Reviews, 1992, 92(5): 995-1006.
[113] 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.
[114] KURODA K, SHIMOJIMA A, KAWAHARA K, et al. Utilization of Alkoxysilyl Groups for the Creation of Structurally Controlled Siloxane-Based Nanomaterials[J]. Chemistry of Materials, 2014, 26(1): 211-220.
[115] XU L-W, CHEN Y, LU Y. Catalytic Silylations of Alcohols: Turning Simple Protecting-Group Strategies into Powerful Enantioselective Synthetic Methods[J]. Angewandte Chemie International Edition, 2015, 54(33): 9456-9466.
[116] ISSA A A, LUYT A S. Kinetics of Alkoxysilanes and Organoalkoxysilanes Polymerization: A Review[J]. Polymers, 2019, 11(3): 537.
[117] REYES-RODRíGUEZ G J, REZAYEE N M, VIDAL-ALBALAT A, et al. Prevalence of Diarylprolinol Silyl Ethers as Catalysts in Total Synthesis and Patents[J]. Chemical Reviews, 2019, 119(6): 4221-4260.
[118] RIEHL J P, RICHARDSON F S. Circularly Polarized Luminescence Spectroscopy[J]. Chemical Reviews, 1986, 86(1): 1-16.
[119] KUMAR J, NAKASHIMA T, KAWAI T. Circularly Polarized Luminescence in Chiral Molecules and Supramolecular Assemblie[J]. The Journal of Physical Chemistry Letters, 2015, 6(17): 3445-3452.
[120] HAN J, GUO S, LU H, et al. Recent Progress on Circularly Polarized Luminescent Materials for Organic Optoelectronic Devices[J]. Advanced Optical Materials, 2018, 6(17): 1800538.
[121] SANG Y, HAN J, ZHAO T, et al. Circularly Polarized Luminescence in Nanoassemblies: Generation, Amplification, and Application[J]. Advanced Materials, 2020, 32(41): 1900110.
[122] ZHAO T, HAN J, DUAN P, et al. New Perspectives to Trigger and Modulate Circularly Polarized Luminescence of Complex and Aggregated Systems: Energy Transfer, Photon Upconversion, Charge Transfer, and Organic Radical[J]. Accounts of Chemical Research, 2020, 53(7): 1279-1292.
[123] INOUYE M, HAYASHI K, YONENAGA Y, et al. A Doubly Alkynylpyrene-Threaded
[4]Rotaxane that Exhibits Strong Circularly Polarized Luminescence from the Spatially Restricted Excimer[J]. Angew Chem Int Ed 2014, 53(52): 14392-14396.
[124] SáNCHEZ-CARNERERO E M, AGARRABEITIA A R, MORENO F, et al. Circularly Polarized Luminescence from Simple Organic Molecules[J]. Chemistry – A European Journal, 2015, 21(39): 13488-13500.
[125] OHISHI Y, INOUYE M. Circularly Polarized Luminescence from Pyrene Excimers[J]. Tetrahedron Letters, 2019, 60(46): 151232.
[126] 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.
[127] ZHAO Z, DAS S, XING G, et al. A 3D Organically Synthesized Porous Carbon Material for Lithium-Ion Batteries[J]. Angewandte Chemie International Edition, 2018, 57(37): 11952-11956.
[128] HART A S, K. C C B, SUBBAIYAN N K, et al. Phenothiazine-Sensitized Organic Solar Cells: Effect of Dye Anchor Group Positioning on the Cell Performance[J]. ACS Applied Materials & Interfaces, 2012, 4(11): 5813-5820.
[129] DRISCOLL P F, DOUGLASS E F, PHEWLUANGDEE M, et al. Photocurrent Generation in Noncovalently Assembled Multilayered Thin Films[J]. Langmuir, 2008, 24(9): 5140-5145.
[130] IGAWA K, YOSHIHIRO D, ICHIKAWA N, et al. Catalytic Enantioselective Synthesis of Alkenylhydrosilanes[J]. Angewandte Chemie International Edition, 2012, 51(51): 12745-12748.
[131] TSUMURA M, IWAHARA T, HIROSE T. Synthesis and Properties of Polycarbosilanes by Hydrosilylation Polymerization[J]. Polymer Journal, 1995, 27(10): 1048-1053.
[132] 潘祖仁. 高分子化学［M］. 北京：化学工业出版社，2007.
[133] 潘祖仁，于在璋，焦书科. 高分子化学［M］. 北京：化学工业出版社2003.
[134] KAKUCHI T, SAKAI R. In Encyclopedia of Polymer Science Technology[M]. 3rd ed., Wiley, Hoboken, 2009, pp. 1-32.
[135] COATES G W. Precise Control of Polyolefin Stereochemistry Using Single-Site Metal Catalysts[J]. Chemical Reviews, 2000, 100(4): 1223-1252.
[136] YASHIMA E, OUSAKA N, TAURA D, et al. Supramolecular Helical Systems: Helical Assemblies of Small Molecules, Foldamers, and Polymers with Chiral Amplification and Their Functions[J]. Chemical Reviews, 2016, 116(22): 13752-13990.
[137] CORNELISSEN J J L M, ROWAN A E, NOLTE R J M, et al. Chiral Architectures from Macromolecular Building Blocks[J]. Chemical Reviews, 2001, 101(12): 4039-4070.
[138] 韩涛，张艺等.具有光学活性高性能高分子材料的研究进展[J]. 高分子材料科学与工程，2011，27（12）：48-56.
[139] ZOU H, WU Q-L, ZHOU L, et al. Chiral Recognition and Resolution Based on Helical Polymers[J]. Chinese Journal of Polymer Science, 2021, 39(12): 1521-1527.
[140] ZHANG Y, DENG J. Chiral Helical Polymer Materials Derived from Achiral Monomers and their Chiral Applications[J]. Polymer Chemistry, 2020, 11(34): 5407-5423.
[141] SHEN J, OKAMOTO Y. Efficient Separation of Enantiomers Using Stereoregular Chiral Polymers[J]. Chemical Reviews, 2016, 116(3): 1094-1138.
[142] SONG L, PAN M, ZHAO R, et al. Recent Advances, Challenges and Perspectives in Enantioselective Release[J]. Journal of Controlled Release, 2020, 324: 156-171.
[143] MANGELINGS D, EELTINK S, VANDER HEYDEN Y Recent Developments in Liquid and Supercritical Fluid Chromatographic Enantioseparations[J]. Handbook of Analytical Separations, 2020, 8, 453-521.
[144] PERCEC V, XIAO Q. Helical Chirality of Supramolecular Columns and Spheres Self-Organizes Complex Liquid Crystals, Crystals, and Quasicrystals[J]. Israel Journal of Chemistry, 2021, 61, 530-556.
[145] NECHVATALOVA M, URBAN J. Current Trends in the Development of Polymer-Based Monolithic Stationary Phases[J]. Analytical Science Advances, 2022, 3, 154-164.
[146] IGAWA K, UEHARA K, KAWASAKI Y, et al. Stereochemical Study on Planar-Chiral Cyclic Molecules using Polysaccharide-Based Column Chromatography[J]. Chirality, 2022, 34(6): 824-832.
[147] YILGöR E, YILGöR I. Silicone Containing Copolymers: Synthesis, Properties and Applications[J]. Progress in Polymer Science, 2014, 39(6): 1165-1195.
[148] ZHU D, HANDSCHUH-WANG S, ZHOU X. Recent Progress in Fabrication and Application of Polydimethylsiloxane Sponges[J]. Journal of Materials Chemistry A, 2017, 5(32): 16467-16497.
[149] HéNOT M, DROCKENMULLER É, LéGER L, et al. Friction of Polymers: from PDMS Melts to PDMS Elastomers[J]. ACS Macro Letters, 2018, 7(1): 112-115.
[150] WOLF M P, SALIEB-BEUGELAAR G B, HUNZIKER P. PDMS with Designer Functionalities–Properties, Modifications Strategies, and Applications[J]. Progress in Polymer Science, 2018, 83: 97-134.
[151] YI B, WANG S, HOU C, et al. Dynamic Siloxane Materials: From Molecular Engineering to Emerging Applications[J]. Chemical Engineering Journal, 2021, 405: 127023.
[152] RUPASINGHE B, FURGAL J C. Degradation of Silicone-Based Materials as a Driving Force for Recyclability[J]. Polymer International, 2022, 71(5): 521-531.
[153] 夏勇，姚洪涛，缪智辉等. 化学进展（Progress in Chemistry），2015，27（5）532-538.
[154] 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.
[155] LI Y, KAWAKAMI Y. Synthesis and Polymerization of an Optically Active Bifunctional Disiloxane. 1. Preparation of Optically Active and Highly Stereoregular Poly[{(1S)-1-(1-naphthyl)-1-phenyl-3,3-dimethyldisiloxane -1,3-diyl}ethylene] by Polyaddition via Hydrosilylation[J]. Macromolecules, 1998, 31(17): 5592-5597.
[156] OISHI M, KAWAKAMI Y. Synthesis of Stereoregular and Optically Active Polysiloxanes Containing 1,3-Dimethyl-1,3-diphenyldisiloxane as a Constitutional Unit[J]. Macromolecules, 2000, 33(6): 1960-1963.
[157] 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.
[158] ZHAI X-Y, WANG X-Q, WU B, et al. Copper-Catalyzed Si-H Bond Insertion Polymerization for Synthesis of Optically Active Polyesters Containing Silicon[J]. Chinese Journal of Chemistry, 2022, 40(1): 21-27.
[159] WEIGEND F. Accurate Coulomb-fitting basis sets for H to Rn[J]. Physical Chemistry Chemical Physics, 2006, 8(9): 1057-1065.
[160] WEIGEND F, AHLRICHS R. Balanced Basis Sets of Split Valence, Triple Zeta Valence and Quadruple Zeta Valence Quality for H to Rn: Design and Assessment of Accuracy[J]. Physical Chemistry Chemical Physics, 2005, 7(18): 3297-3305.
[161] LU T, CHEN F. Multiwfn: A Multifunctional Wavefunction Analyzer[J]. Journal of Computational Chemistry, 2012, 33(5): 580-592.
[162] WORCH J C, PRYDDERCH H, JIMAJA S, et al. Stereochemical Enhancement of Polymer Properties[J]. Nature Reviews Chemistry, 2019, 3(9): 514-535.
[163] BOAEN N K, HILLMYER M A. Post-Polymerization Functionalization of Polyolefins[J]. Chemical Society Reviews, 2005, 34(3): 267-275.
[164] GAUTHIER M A, GIBSON M I, KLOK H-A. Synthesis of Functional Polymers by Post-Polymerization Modification[J]. Angewandte Chemie International Edition, 2009, 48(1): 48-58.
[165] STEINBACH T, WURM F R. Poly(phosphoester)s: A New Platform for Degradable Polymers[J]. Angewandte Chemie International Edition, 2015, 54(21): 6098-6108.
[166] PESENTI T, NICOLAS J. 100 th Anniversary of Macromolecular Science Viewpoint: Degradable Polymers from Radical Ring-Opening Polymerization: Latest Advances, New Directions, and Ongoing Challenges [J]. ACS Macro Letters, 2020, 9(12): 1812-1835.
[167] PELLIS A, MALINCONICO M, GUARNERI A, et al. Renewable Polymers and Plastics: Performance Beyond the Green[J]. New Biotechnology, 2021, 60: 146-158.
[168] CHENG C, WATTS A, HILLMYER M A, et al. Polysilylether: A Degradable Polymer from Biorenewable Feedstocks[J]. Angewandte Chemie International Edition, 2016, 55(39): 11872-11876.
[169] FOUILLOUX H, RAGER M-N, RíOS P, et al. Highly Efficient Synthesis of Poly(silylether)s: Access to Degradable Polymers from Renewable Resources[J]. Angewandte Chemie International Edition, 2022, 61(7): e202113443.
[170] GHAVTADZE N, MELKONYAN F S, GULEVICH A V, et al. Conversion of 1-Alkenes into 1,4-Diols Through an Auxiliary-Mediated Formal Homoallylic C–H Oxidation[J]. Nature Chemistry, 2014, 6(2): 122-125.
[171] SANGTRIRUTNUGUL P, TILLEY T D. Silyl Derivatives of [Bis (8-quinolyl)methylsilyl]iridium(III) Complexes:  Catalytic Redistribution of Arylsilanes and Dehydrogenative Arene Silylation[J]. Organometallics, 2007, 26(23): 5557-5568.
[172] KOMURO T, KITANO T, YAMAHIRA N, et al. Directed ortho-C–H Silylation Coupled with trans-Selective Hydrogenation of Arylalkynes Catalyzed by Ruthenium Complexes of a Xanthene-Based Si,O,Si-Chelate Ligand, “Xantsil”[J]. Organometallics, 2016, 35(9): 1209-1217.
[173] KITANO T, KOMURO T, ONO R, et al. Tandem Hydrosilylation/o-C–H Silylation of Arylalkynes Catalyzed by Ruthenium Bis(silyl) Aminophosphine Complexes[J]. Organometallics, 2017, 36(15): 2710-2713.
[174] YANG B, TAN X, GE Y, et al. Stereodivergent Asymmetric Synthesis of P-Atropisomeric Si-Stereogenic Monohydrosilanes[J]. Organic Chemistry Frontiers, 2023, 10(19): 4862-4870.
[175] YANG B, GAO J, TAN X, et al. Chiral PSiSi-Ligand Enabled Iridium-Catalyzed Atroposelective Intermolecular C–H Silylation[J]. Angewandte Chemie International Edition, 2023, 62(36): e202307812.