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ケイ素は地殻に豊富に存在する元素であるため、有機合成や材料科学、および創薬における有効活用が期待されています。私たちは、遷移金属触媒による含ケイ素σ結合の活性化に基づいた、新しい触媒的シリル化反応の開発に取り組んでいます。  
**ビスシリル化
一例として、分子内ビスシリル化を示します。この反応は、Si-Si結合の活性化に有効な新しいパラジウム触媒「パラジウム-イソニトリル触媒」を見出すことにより、開発に成功しました。[Ref .1] 分子内ビスシリル化を応用し、キラルなアリルシラン[Ref. 2]、アレニルシラン[Ref. 3]、およびポリオール[Ref. 4]の立体選択的合成を達成しています。  
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**シリルホウ素化
遷移金属触媒存在下においてSi-B結合が特徴的な反応性と選択性で不飽和炭化水素などと反応することを見出しました。[Ref. 5] これまでに開発した触媒反応は、(1) シンプルな付加反応（シリルホウ素化）[Ref. 6]、(2) シリルホウ素化C–Cカップリング反応[Ref. 7]、(3) 小員環のシリルホウ素化C–C切断[Ref. 8]、の三つに分類できます。さらに最近では、ケイ素上に官能基を有するシリルボランの合成法を確立し[Ref. 9, see also Ref. 10]、（ジアルキルアミノ）シリルボランがシリレンの合成等価体として利用できることを明らかにしました。[Ref. 11] これまでに開発した反応の例を以下に示します。  
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**参考文献
-Ref. 1
--Palladium-Catalyzed Insertion of Isocyanides into the Silicon-Silicon Linkages of Oligosilanes Y. Ito, M. Suginome, T. Matsuura, M. Murakami, '''J. Am. Chem. Soc.''' ''1991'', 113, 8899-8908, [[10.1021/ja00023a043>http://dx.doi.org/10.1021/ja00023a043]]
--Palladium(II) Acetate–tert-Alkyl Isocyanide as a Highly Efficient Catalyst for the Inter- and Intramolecular Bis-silylation of Carbon-Carbon Triple Bonds Y. Ito, M. Suginome, M. Murakami, '''J. Org. Chem.''' ''1991'', 56, 1948-1951, [[10.1021/jo00005a055>http://dx.doi.org/10.1021/jo00005a055]]
--Intramolecular Bis-silylation of Carbon-Carbon Double Bonds Leading to Stereoselective Synthesis of 1,2,4-Triols M. Murakami, P. G. Andersson, M. Suginome, Y. Ito, '''J. Am. Chem. Soc.''' ''1991'', 113, 3987-3988, [[10.1021/ja00010a049>http://dx.doi.org/10.1021/ja00010a049]]
--Stereoselective Intramolecular Bis-Silylation of Alkenes Promoted by Palladium-Isocyanide Catalyst Leading to Polyol Synthesis M. Murakami, M. Suginome, K. Fujimoto, H. Nakamura, P. G. Andersson, Y. Ito, '''J. Am. Chem. Soc.''' ''1993'', 115, 6487-6498, [[10.1021/ja00068a003>http://dx.doi.org/10.1021/ja00068a003]]
--Synthesis and Structure of a Nontwisted Tetrakis(organosilyl)ethenes M. Murakami, M. Suginome, K. Fujimoto, Y. Ito, '''Angew. Chem., Int. Ed. Engl.''' ''1993'', 32, 1473-1475, [[10.1002/anie.199314731>http://dx.doi.org/10.1002/anie.199314731]], '''Angew. Chem.''' ''1993'', 105, 1542-1544, [[10.1002/ange.19931051041>http://dx.doi.org/10.1002/ange.19931051041]]
--Novel Activation of Two Si–Si σ-Bonds in a Molecule by tert-Alkyl Isocyanide–Palladium Complexes M. Suginome, H. Oike, Y. Ito, '''Organometallics''' ''1994'', 13, 4148-4150, [[10.1021/om00023a009>http://dx.doi.org/10.1021/om00023a009]]
--Macrocycles with Regularly Arranged Si–Si Bonds: Ring-Enlargement Oligomerization of Cyclic Disilanes via Palladium-Catalyzed Si-Si σ-Bond Metathesis. M. Suginome, H. Oike, Y. Ito, '''J. Am. Chem. Soc.''' ''1995'', 117, 1665-1666, [[10.1021/ja00110a034>http://dx.doi.org/10.1021/ja00110a034]]
--Reactions of Si–Si σ-Bonds with Bis(t-alkyl isocyanide)palladium(0) Complexes. Synthesis and Reactions of Cyclic Bis(organosilyl)palladium Complexes [Headline Article] M. Suginome, H. Oike, S.-S. Park, Y. Ito, '''Bull. Chem. Soc. Jpn.''' ''1996'', 69, 289–299, [[10.1246/bcsj.69.289>http://dx.doi.org/10.1246/bcsj.69.289]]
--Reactions of a Spiro Trisilane with Palladium Complexes: Synthesis and Structure of Tris(organosilyl))Cp Pd(IV) and Bis(organosilyl)(μ-organosilylene)Pd2(II) Complexes. M. Suginome, Y. Kato, N. Takeda, H. Oike, Y. Ito, '''Organometallics''' ''1998'', 17, 495-497, [[10.1021/om9710778>http://dx.doi.org/10.1021/om9710778]]
-Ref. 2
--New Synthesis of (E)-Allylsilanes with High Enantiopurity via Diastereoselective Intramolecular Bis-Silylation of Chiral Allylic Alcohols M. Suginome, A. Matsumoto, Y. Ito, '''J. Am. Chem. Soc.''' ''1996'', 118, 3061–3062, [[10.1021/ja954251x>http://dx.doi.org/10.1021/ja954251x]]
--Synthesis of Highly Enantio-enriched Allylsilanes via Palladium-catalyzed Intramolecular Bis-Silylation.  Determination of the Enantiomeric Excesses through Regio- and Stereoselective Hydroboration with 9-BBN.   M. Suginome, T. Iwanami, A. Matsumoto, Y. Ito, '''Tetrahedron: Asymmetry''', ''1997'', 8, 859-862, [[10.1016/S0957-4166(97)00073-6>http://dx.doi.org/10.1016/S0957-4166(97)00073-6]]
--Stereoselective Cyclization of Highly Enantio-Enriched Allylsilanes with Aldehydes via Acetal Formation: New Asymmetric Access to Tetrahydropyrans and Piperidines M. Suginome, T. Iwanami, Y. Ito, '''J. Org. Chem.''' ''1998'', 63, 6096-6097, [[10.1021/jo981173y>http://dx.doi.org/10.1021/jo981173y]]
--Asymmetric Synthesis of 2,3-Disubstituted Oxepanes via Acetalization-Cyclization of an Enantioenriched Functionalized Allylsilane with Aldehydes M. Suginome, T. Iwanami, Y. Ito, '''Chem. Commun.''' ''1999'', 2537-2538, [[10.1039/a908603j>http://dx.doi.org/10.1039/a908603j]]
--Asymmetric Synthesis of Cyclic Alkenes via Cyclization of Enantioenriched Allylsilanes M. Suginome, T. Iwanami, A. Yamamoto, and Y. Ito, '''Synlett''', ''2001'', 1042-1045, [[10.1055/s-2001-14656>http://dx.doi.org/10.1055/s-2001-14656]]
--Solid-Phase Synthesis and Asymmetric Reactions of Polymer-Supported Highly Enantioenriched Allylsilanes M. Suginome, T. Iwanami, and Y. Ito, '''J. Am. Chem. Soc.''' ''2001'', 123, 4356-4357, [[10.1021/ja005865r>http://dx.doi.org/10.1021/ja005865r]]
--Stereoselective Synthesis of Highly Enantioenriched (E)-Allylsilanes by Palladium-Catalyzed Intramolecular Bis-Silylation: 1,3-Chirality Transfer and Enantienrichment via Dimer Formation M. Suginome, T. Iwanami, Y. Ohmori, A. Matsumoto, Y. Ito, '''Chem. Eur. J.''', ''2005'', 11, 2954-2965, [[10.1002/chem.200401031>http://dx.doi.org/10.1002/chem.200401031]]
-Ref. 3
--Palladium-Catalyzed Intramolecular Bis–Silylation of Propargylic Alcohols: A New Stereospecific Access to Chiral Allenylsilanes M. Suginome, A. Matsumoto, Y. Ito, '''J. Org. Chem.''' ''1996'', 61, 4884-4885, [[10.1021/jo960778w>http://dx.doi.org/10.1021/jo960778w]]
-Ref. 4
--Diastereoselective Intramolecular Bis-Silylation of a Carbon-Carbon Double Bond.  A Highly Stereocontrolled Synthesis of (-)-Avenaciolide M. Suginome, Y. Yamamoto, K. Fujii, Y. Ito, '''J. Am. Chem. Soc.''' ''1995'', 117, 9608–9609, [[10.1021/10.1021/ja00142a047>http://dx.doi.org/10.1021/ja00142a047]]
--Intramolecular Bis-Silylation of Alkenes Catalyzed by Palladium(0) tert-alkyl isocyanide Complex.  Stereoselective Synthesis of Polyols Y. Ito, M. Suginome, '''Pure Appl. Chem.''' ''1996'', 68, 505-508, [[10.1351/pac199668030505>http://dx.doi.org/10.1351/pac199668030505]]
-Ref. 5
--Silylboranes as New Tools in Organic Synthesis T. Ohmura, M. Suginome, '''Bull. Chem. Soc. Jpn.''' ''2009'', '''82''', 29-49, [[10.1246/bcsj.82.29>http://dx.doi.org/10.1246/bcsj.82.29]]
-Ref. 6
--Regio- and Stereoselective Silaboration of Alkynes Catalyzed by Palladium and Platinum Complexes M. Suginome, H. Nakamura, Y. Ito, '''Chem. Commun.''', ''1996'', 2777–2778, [[10.1039/CC9960002777>http://dx.doi.org/10.1039/CC9960002777]]
--Platinum-catalyzed Regioselective Silaboration of Alkenes. M. Suginome, H. Nakamura, Y. Ito, '''Angew. Chem. Int. Ed. Engl.''' ''1997'', 36, 2516-2518, [[10.1002/anie.199725161>http://dx.doi.org/10.1002/anie.199725161]], '''Angew. Chem.''' 1997, 109, 2627-2628, [[10.1002/ange.19971092237>http://dx.doi.org/10.1002/ange.19971092237]]
--Regio- and Stereoselective Synthesis of (Z)-β-Silylalkenylboranes by Silaboration of Alkynes Catalyzed by Palladium and Platinum Complexes M. Suginome, T. Matsuda, H. Nakamura, Y. Ito, '''Tetrahedron''' ''1999'', 55, 8787-8800, [[10.1016/S0040-4020(99)00444-5>http://dx.doi.org/10.1016/S0040-4020(99)00444-5]]
--Highly Regioselective Silaboration of 3-Substituted 1,2-Dienes Catalyzed by Palladium/2,6-Xylyl Isocyanide M. Suginome, Y. Ohmori, Y. Ito, '''Synlett''' ''1999'', 1567-1568, [[10.1055/s-1999-2917>http://dx.doi.org/10.1055/s-1999-2917]]
--Stereoselective 1,4-Silaboration of 1,3-Dienes Catalyzed by Nickel Complexes M. Suginome, T. Matsuda, T. Yoshimoto, Y. Ito, '''Org. Lett.''' ''1999'', 1, 1567-1569, [[10.1021/ol990908y>http://dx.doi.org/10.1021/ol990908y]]
--Synthesis of (Boryl)(silyl)iminomethanes by Insertion of Isonitriles into Silicon-Boron Bonds M. Suginome, T. Fukuda, H. Nakamura, Y. Ito, '''Organometallics''' ''2000'', 19, 719-721, [[10.1021/om9909136>http://dx.doi.org/10.1021/om9909136]]
--Palladium-Catalyzed Regioselective Silaboration of 1,2-Dienes M. Suginome, Y. Ohmori, Y. Ito, '''J. Organomet. Chem.''' ''2000'', 611, 403-413 (Special issue: The Chemistry of Interelement Linkage), [[10.1016/S0022-328X(00)00472-1>http://dx.doi.org/10.1016/S0022-328X(00)00472-1]]
--β-Borylallylsilanes as a New Tool for Convenient Synthesis of Alkenylboranes M. Suginome, Y. Ohmori, and Y. Ito, '''J. Am. Chem. Soc.''' ''2001'', 123, 4601-4602, [[10.1021/ja0058381>http://dx.doi.org/10.1021/ja0058381]]
--Stereoselective construction of trans-1,2-benzooxadecaline frameworks by three-component cascade reactions of an α-phenethyl-β-borylallylsilane with aldehydes M. Suginome, Y. Ohmori, Y. Ito, '''Chem. Commun.''' ''2001'', 1090-1091, [[10.1039/b102613p>http://dx.doi.org/10.1039/b102613p]]
--Enantioface-Selective Palladium-Catalyzed Silaboration of Allenes via Double Asymmetric Induction M. Suginome, T. Ohmura, Y. Miyake, S. Mitani, Y. Ito, M. Murakami, '''J. Am. Chem. Soc.''' ''2003'', 125, 11174-11175, [[10.1021/ja0368958>http://dx.doi.org/10.1021/ja0368958]]
--The Asymmetric Silaboration of Terminal Allenes Bearingα-Stereogenic Centers: Stereoselection Based on “Reagent Control” T. Ohmura, M. Suginome, '''Org. Lett.''' ''2006'', 8, 2503–2506, [[10.1021/ol060666j>http://dx.doi.org/10.1021/ol060666j]]
--Palladium-Catalyzed Asymmetric Silaboration of Allenes T. Ohmura, H. Taniguchi, M. Suginome, '''J. Am. Chem. Soc.''' ''2006'', 128, 13682-13683, [[10.1021/ja063934h>http://dx.doi.org/10.1021/ja063934h]]
--Ligand-Controlled, Complementary Stereoselectivity in the Platinum-Catalyzed Intramolecular Silaboration of Alkenes T. Ohmura, H. Furukawa, M. Suginome, '''J. Am. Chem. Soc.''' ''2006'', 128, 13366-13367, [[10.1021/ja065588+>http://dx.doi.org/10.1021/ja065588+]]
--A Mechanism for the Palladium–Catalyzed Regioselective Silaboration of Allene: A Theoretical Study Y. Abe, K. Kuramoto, M. Ehara, H. Nakatsuji, M. Suginome, M. Murakami, Y. Ito, '''Organometallics''' ''2008'', 27, 1736-1742, [[10.1021/om070110f>http://dx.doi.org/10.1021/om070110f]]
-Ref. 7
--Platinum-Catalyzed Silaborative Coupling of 1,3-Dienes to Aldehydes:  Regio- and Stereoselective Allylation with Dienes through Allylic Platinum Intermediates M. Suginome, H. Nakamura, T. Matsuda, Y. Ito, '''J. Am. Chem. Soc.''' ''1998'', 120, 4248-4249, [[10.1021/ja980373o>http://dx.doi.org/10.1021/ja980373o]]
--Nickel-Catalyzed Silaborative Dimerization of Alkynes M. Suginome, T. Matsuda, Y. Ito, '''Organometallics''' ''1998'', 17, 5233-5235, [[10.1021/om9807250>http://dx.doi.org/10.1021/om9807250]]
-Ref. 8
--Palladium- and Platinum-Catalyzed Silaboration of Methylenecyclopropanes through Selective Proximal or Distal C-C Bond Cleavage M. Suginome, T. Matsuda, and Y. Ito, '''J. Am. Chem. Soc.''' ''2000'', 122, 11015-11016, [[10.1021/ja002885k>http://dx.doi.org/10.1021/ja002885k]]
--Nickel-Catalyzed Silaboration of Small-Ring Vinylcycloalkanes: Regio- and Stereoselective (E)-Allylsilane Formation via C-C Bond Cleavage.     M. Suginome, T. Matsuda, T. Yoshimoto, Y. Ito, '''Organometallics'''  ''2002'', 21, 1537-1539, [[10.1021/om020007k>http://dx.doi.org/10.1021/om020007k]]
--Palladium-Catalyzed Asymmetric Silaborative C–C Cleavage of meso-Methylenecyclopropanes T. Ohmura, H. Taniguchi, Yoshiyuki Kondo, M. Suginome, '''J. Am. Chem. Soc.''' ''2007'', 129, 3518-3519, [[10.1021/ja0703170>http://dx.doi.org/10.1021/ja0703170]]
-Ref. 9
--Synthesis of Silylboronic Acid Esters Functionalized on Silicon T. Ohmura, K. Masuda, Hideki Furukawa, M. Suginome, '''Organometallics''' ''2007'', 26, 1291-1294, [[10.1021/om0609867>http://dx.doi.org/10.1021/om0609867]]
-Ref. 10
--Convenient Preparation of Silylboranes M. Suginome, T. Matsuda, and Y. Ito, '''Organometallics''' ''2000'', 19, 4647-4649, [[10.1021/om000254t>http://dx.doi.org/10.1021/om000254t]]
--Synthesis and Reactions of Cyclic Silylboranes M. Suginome, H. Noguch, T. Hasui, and M. Murakami, '''Bull. Chem. Soc. Jpn''', ''2005'', 78, 323-326, [[10.1246/bcsj.78.323>http://dx.doi.org/10.1246/bcsj.78.323]]
-Ref. 11
--Silylboranes Bearing Dialkylamino Groups on Silicon as Silylene Equivalents: Palladium-Catalyzed Regioselective Synthesis of 2,4-Disubstituted Siloles	T. Ohmura, K. Masuda, M. Suginome, '''J. Am. Chem. Soc.''' ''2008'', 130, 1526-1527, [[10.1021/ja073896h>http://dx.doi.org/10.1021/ja073896h]]
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