シリカ担持かご型トリアルキルホスフィンによる協奏機能触媒 Concerted Catalysis with Silica-Supported, Caged Trialkylphosphine 北海道大学大学院理学研究院化学部門 澤村 正也 １．はじめに 䇭䇭⸅ᇦᯏ⢻䉕ᜬ䈧นṁᕈ㊄ዻ㍲䈱࿕㕙䈻䈱࿕ቯൻ䈲䇮 ⸅ᇦ䈱࿁ౣ↪ᕈะ䈱⋡⊛䈪ฎ䈒䈎䉌 ข䉍䉏䉌䉏䈩䈐䈢⸅ᇦ⸳⸘䈱ᣇᴺ⺰䈪䈅䉎䇯 䈚䈎䈚䇮 䈖䈉䈚䈩ᓧ䉌䉏䉎⸅ᇦ䈲ኻᔕ䈜䉎นṁᕈ⸅ᇦ䈫Ყセ䈚 䈩ૐᵴᕈ䈪䈅䉎䈖䈫䈏ᄙ䈒䇮 ࿕ቯൻ䈮䉋䉍ᵴᕈ䈏ะ䈜䉎䈖䈫䈲䈾䈫䉖䈬䈭䈇䇯 ᵴᕈૐਅ䈱ਥ䈭ේ࿃䈲䇮 ࿕ቯ ⋧䉇䊥䊮䉦䊷ㇱ䈮䉋䉎┙㓚ኂ䈪䈅䉎䇯 ᵴᕈਛᔃ䈱䉁䉒䉍䈱ⓨ㑆䈏䇮 ਛᔃ㊄ዻ䈮⚿ว䈚䈢㈩ሶ䈱┙ല ᨐ䈪⼔䈘䉏䈩䈇䉎႐ว䈮䈲䇮 䈖䈱䉋䈉䈭㒖ኂലᨐ䈏䈍䉋䈳䈭䈇䇯 䈚䈎䈚䈖䈱႐ว䇮 ᵴᕈਛᔃ䈱ᕈ⾰䈏ర䈱 ဋ৻♽䈫ᄢ䈐䈒ᄌ䉒䉎䈖䈫䈲䈭䈇䈣䉐䈉䇯 䇭䇭ᚒ䇱䈲䇮 ㈩ะ䉕ⷙቯ䈪䈐䉎ㆡಾ䈭㈩ሶ䈫࿕䈇ၮ⋚䉕↪䈇䈩ᵴᕈਛᔃ䉕䊋䊦䉪䈮๒␜䈜䉏䈳䇮 ㊄ዻਛᔃ 䈱ᵴᕈ䉕ᜬ䈪䈐䇮 䈘䉌䈮䉮䊮䊌䉪䊃䈭㈩ሶ䉕↪䈇䉎䈖䈫䈮䉋䉍䇮 ࿕㕙䈱ᯏ⢻䈫ಽሶ⸅ᇦ䈱ᯏ⢻䉕දᄼ ⊛䈮Ⲣว䈜䉎䈖䈫䈏䈪䈐䉎䈫⠨䈋䈢䇯 䈠䈖䈪䇮 䉮䊮䊌䉪䊃䈪⋥䈭᭴ㅧ䉕ᜬ䈤䇮 ㈩ਛᔃㄭற䈱᭴ㅧੂ䉏䉕ᦨ ዊ㒢䈮䈤䈭䈏䉌ൻቇୃ㘼䉕ᣉ䈜䈖䈫䈱䈪䈐䉎ᯏ⢻ᕈ䊖䉴䊐䉞䊮㈩ሶ䈫䈚䈩䇮 䈎䈗ဳ䊖䉴䊐䉞䊮 SMAP 䉕㐿 ⊒䈚䈢 [1,2]䇯 ᧄ․ቯ㗔ၞ⎇ⓥ䈪䈲㊄ዻ㍲ಽሶ䈫࿕㕙䈏දᄼ⊛䈮ᯏ⢻䈜䉎⸅ᇦ 䋨ಽሶ㺍㕙දᄼᯏ⢻ ⸅ᇦ䋩 䈱㐿⊒䉕ౕൻ䈜䉎䈢䉄䈱৻䈧䈱ᣇᴺ䈫䈚䈩䇮 SMAP ᭴ㅧ䉕⋥ធ䉲䊥䉦㕙䈮⚿ว䈘䈞䈢 [silica]- SMAP 䉕㐿⊒䈚䈢 [3]䇯 䈠䈱 Rh ⶄว䈲䇮 䉬䊃䊮䈱䊍䊄䊨䉲䊥䊦ൻᔕ䈮ᭂ䉄䈩㜞䈇⸅ᇦᵴᕈ䈫ఝ䉏䈢࿁ ౣ↪ᕈ䉕␜䈚䈢䇯 䈖䈱⸅ᇦ䈲┙㓚ኂ䈱ᄢ䈐䈇ᔕ䈮ᭂ䉄䈩ല䈪䈅䉍䇮 (t-Bu)2C=O 䈫 (t-Bu)Me2SiH 䈱ᔕ䉅ቶ᷷䈪ㅴⴕ䈜䉎䈾䈬䈪䈅䉎䇯 ࿕⸅ᇦ䇮 ဋ৻♽⸅ᇦ䈱䈬䈤䉌䈮䉅䈭䈚䈋䈭䈇ಽሶᄌ឵䈪䈅䉎䇯 ２．かご型ホスフィン SMAP のシリカゲル担持と錯体化 [3] 䇭䇭䈎䈗ဳ䊖䉴䊐䉞䊮 SMAP 䈱䉲䊥䉦䉭䊦䈻䈱ᜂᜬ䈲 䌛Scheme 1䌝 䈱䈫䈍䉍ⴕ䈦䈢䇯 䉬䉟⚛ේሶ䈮 Ph ၮ 䉕ᜬ䈧 SMAP 䈱ⷫൻว‛ Ph-SMAP[1] 䉕䊃䊥䊐䊦䉥䊨䊜䉺䊮䉴䊦䊖䊮㉄䈪ಣℂ䈜䉎䈖䈫䈪䉲䊥䊦䉦䉼䉥䊮⒳ 䉕⊒↢䈘䈞䉎 [2]䇯 䈖䉏䉕䉲䊥䉦䉭䊦 (CARiACT Q-10) 㕙䈱䉲䊤䊉䊷䊦ၮ䈫ᔕ䈘䈞䇮 Ⴎၮಣℂ䇮 ⌀ⓨ ടᾲੇ῎䈜䉎䈖䈫䈮䉋䉍 SMAP ࿕ቯൻ䉲䊥䉦䉕ᓧ䈢䇯 ⛯䈇䈩䊃䊥䊜䉼䊦䉲䊥䊦䉟䊚䉻䉹䊷䊦䈪ಣℂ䈜䉎䈖䈫䈮䉋 䉍䇮 ᧂୃ㘼䈱㕙䉲䊤䊉䊷䊦䉕 TMS 䉣䊮䊄䉨䊞䉾䊒䈚䇮 ౣ䈶⌀ⓨടᾲੇ῎䈜䉎䈖䈫䈪䇮 એᓟ䈱⎇ⓥ䈮↪䈇䉎 [silica]-SMAP 䉕ᓧ䈢䇯 䇭䇭[silica]-SMAP 䈱㍲ൻ䈲䇮 ㆊ䈱೨㚟䈫ᯏṁᇦਛᷙว䈚䇮 ᶧጀ䉕ಽ㔌ᓟ䇮 ࿕ᚑಽ䉕ᯏṁᇦ 䈪ᵞᵺ䈜䉎䈖䈫䈪ⴕ䈋䉎䇯 [RhCl(cod)]2 䈫䈱ᔕ䈮䉋䉎㍲ᒻᚑ䈮䈧䈇䈩䈚䈒ᬌ⸛䈚䇮 P/Rh ᷙวᲧ䈮䉋䉌 䈝䇮 P–Rh 1:1 ㍲ [silica]-SMAP–RhCl(cod) 䈏ㆬᛯ⊛䈮ᓧ䉌䉏䉎䈖䈫䉕⏕䈚䈢䇯 䈢䈫䈋䈳 P ㆊ᧦ઙ 䈪 [silica]-SMAP 䈫 [RhCl(cod)]2 䉕㍲ᒻᚑ䈘䈞䇮 ࿕ NMR 䉕᷹ቯ䈚䈢႐ว䇮 P–Rh 1:1 ㍲䈮↱᧪䈜䉎 䉲䉫䊅䊦䈫㈩ሶ䈮↱᧪䈜䉎䉲䉫䊅䊦䈏หᤨ䈮᷹ⷰ䈘䉏䈢 䌛Figure 1䌝䇯 ㆊ䈱䊖䉴䊐䉞䊮䈏ሽ䈚䈩䉅 Rh ਛᔃ䈮╙ 2 䈱䊖䉴䊐䉞䊮䈏㈩䈚䈭䈇䈖䈫䉕␜䈚䈩䈇䉎䇯 ３．シリカ担持 SMAP-Rh 触媒によるケトンのヒドロシリル化 [3] 䇭䇭[silica]-SMAP 䈫 [RhCl(C2H4)2]2 Table 1: Hydrosilylation of Ketones Catalyzed by Rh–[silica]-SM AP.[a] 䈎 䉌 ⺞ 䈚 䈢 ࿕ ቯ ൻ Rh ㍲ 䈲䇮 䉬䊃䊮䈱䊍䊄䊨䉲䊥䊦ൻᔕ䈮㕖Ᏹ O R1 R2 + HSiR 3 䈮㜞䈇⸅ᇦᵴᕈ䉕␜䈚䈢 䌛Table 1䌝䇯 䈖䈱⸅ᇦᔕ䈲ၮ⾰䈱㜞 [RhCl(CH 2 =CH 2 ) 2 ]2 (0.5 m ol % ) [silica]-SMAP (1.0 mol %) OSiR 3 R1 benzene, rt (23–25 °C) R2 tim e [b] yield, % HSiMe 2 Ph <5 m in 94 [c] 2 HSiEt3 <5 m in 99 [c] Bu)Me2SiH 䈱 ᔕ 䈏䇮 1mol% 3 HSi(t-Bu)M e 2 <5 m in 99 [c] (Rh) 䈱⸅ᇦሽਅ䇮 ቶ᷷䇮 12 ᤨ 4 HSiMe 2 Ph 10 min 100 [c] 㑆䈪ቯ㊂⊛䈮ㅴⴕ䈜䉎䈾䈬䈪䈅䉎䇯 5 HSiEt3 1h 99 [c] 䇭䇭[silica]-SMAP–Rh ⸅ ᇦ 䈲 ⸅ ᇦ 6 HSi(t-Bu)M e 2 4h 100 [c] ኼ䋯࿁ౣ↪ᕈ䈮䈍䈇䈩䉅․ 7 42 h 94 [c] ╩䈜䈼䈐ᕈ⢻䉕ᜬ䈦䈩䈇䉎䇯 ṁᶧ 8 HSiEt3 4h 96 [d] ਛ䈻䈱 Rh 䈱ᶐ䉂䈚䈲䈾䈫䉖䈬 9 HSi(t-Bu)M e 2 12 h 97 [d] entry ketone 䈘䈮ኻ䈜䉎ኡኈᕈ䈮㑐䈚䈩․䈮ఝ 1 O 䉏 䈩 䈇 䉎䇯 (tert-Bu)2C=O 䈫 (tert- ᷹ⷰ䈘䉏䈭䈇䇯 ਇᵴᕈ䉧䉴㔓࿐᳇ ਅ䈪ข䉍ᛒ䈦䈩䈇䉎㒢䉍ᄬᵴ䈲䈍䈖 䉌䈝䇮 䉐ㆊ䋯ᵞᵺᠲ䉕ⴕ䈉䈣䈔 O O hydrosilane HSiMe 2 Ph [a] Conditions: Ketone (1 mmol), HSiR3 (1.2 mmol), [RhCl(C2 H4 )2 ]2 (0.005 mmol), [silica]-SMAP (0.010 mmol), benzene (1 mL). Conversion of ketone is 100% in all entries. [b] Approximate time required for 100% conversion. [c] GC yield. [d] Isolated yield. 䈪䇮 ➅䉍䈚↪䈜䉎䈖䈫䈏䈪䈐䈢䇯 ４．シリカ担持 SMAP-Rh(Ir) 触媒によるケトン ( アルケン ) の水素化 䇭䇭[silica]-SMAP–Rh ⸅ᇦ䈲䉬䊃䊮䈱᳓⚛ൻ䈮ኻ䈚䈩䉅㜞ᵴᕈ䈪䈅䉎䇯 䊍䊄䊨䉲䊥䊦ൻ䈫ห᭽䈮䇮 㜞䈇䉬䊃䊮 䈱ᔕ䈻䈱ఝ䉏䈢ㆡ↪ᕈ䈏ᄢ䈐䈭․ᓽ䈪䈅䉎䇯 (i-Pr)2C=O 䈱᳓⚛ൻ䈏 0.5 mol% (Rh) 䈱⸅ᇦሽਅ䇮 ೋ ᦼ᳓⚛ 5 ᳇䇮 ቶ᷷䇮 3 ᤨ㑆䈪ቯ㊂⊛䈮ㅴⴕ䈚䈢 䌛Scheme 2䌝䇯 䈖䈱䉋䈉䈭㜞䈇ၮ⾰䈱᳓⚛ൻ䈮ᵴᕈ 䉕␜䈜⸅ᇦ♽䈲ဋ৻♽䇮 ਇဋ৻♽䈱䈬䈤䉌䈮䈍䈇䈩䉅ᭂ䉄䈩㒢䉌䉏䈩䈍䉍䇮 䈇䈝䉏䈱䈮䈍䈇䈩䉅䇮 㜞᷷䇮 㜞䈱䈎䈭䉍෩䈚䈇ᔕ᧦ઙ䉕ᔅⷐ䈫䈜䉎䈖䈫䈏ႎ๔䈘䉏䈩䈇䉎䇯 䈘䉌䈮㜞䈇ၮ⾰䈪䈅䉎 (tert-Bu)2C=O 䉅䇮 ᳓⚛ 30 ᳇䇮 100 㫦C䇮 3 ᤨ㑆䈪ቯ㊂⊛䈮ㅴⴕ䈚䈢 䌛Scheme 3䌝 䇭䇭[silica]-SMAP 䈫 [IrCl(cod)]2 䈎䉌⺞䈚䈢࿕ቯൻ Ir ⸅ᇦ䈲㜞䈇䉝䊦䉬䊮䈱᳓⚛ൻ䈮ല䈪䈅䉎䇯 䋴⟎ ឵䉝䊦䉬䊮䈪䈅䉎 Me2C=CMe2 䈱᳓⚛ൻ䈲䇮 1mol% (Ir) 䈱⸅ᇦሽਅ䇮 ᳓⚛ 1 ᳇䇮 ቶ᷷䇮 4 ᤨ㑆䈪 ቯ㊂⊛䈮ㅴⴕ䈚䈢 䌛Scheme 4䌝䇯 㜞䈇䉝䊦䉬䊮䈱᳓⚛ൻ䈮䈲䉦䉼䉥䊮ᕈ Ir ⸅ᇦ 䋨Crabtree ⸅ᇦ䋩 䉕㕖 ㈩ᕈ䈱ṁᇦਛ䈪↪䈇䉎ᚻᴺ䈏৻⥸⊛䈪䈅䉎䈏䇮 ᧄ⸅ᇦ♽䈪䈲ᐢ᳢䈭ṁᇦ䉕↪䈜䉎䈖䈫䈏น⢻䈪䈅䉎䇯 参考文献 [1] A. Ochida, K. Hara, H. Ito, M. Sawamura, Org. Lett., 5, 2671–2672 (2003). [2] A. Ochida, S. Ito, T. Miyahara, H. Ito, M. Sawamura, Chem. Lett., 35, 294–295 (2006). [3] G. Hamasaka, A. Ochida, K. Hara, M. Sawamura, Angew. Chem. Int. Ed., 46, 5381–5383 (2007). Concerted Catalysis with Silica-Supported, Caged Trialkylphosphine Masaya Sawamura A least sterically demanding, caged trialkylphosphine (SMAP)[1,2] was immobilized on a silica gel surface ([silica]-SMAP) through a linker wit a minimum conformational flexibility (Scheme 1). The immobilized phosphine showed a unique coordination behavior to form a 1:1 Rh–P complex. It was used as a platform to create a highly active catalytic center. A heterogeneous catalysts, prepared from [silica]-SMAP and [RhCl(C2H4)2]2 showed an exceptionally high activity for the hydrosilylation of sterically hindered ketones, as represented by the transformations of di(tert-butyl) ketones into the corresponding (t-Bu)Me2Si-protected secondary alcohols at ambient temperature (Scheme 2). These transformations have not been achieved with any other catalyst system to date. The [silica]-SMAP–Rh(Ir) systems are also effective for hindered cases of the catalytic hydrogenation of ketones and alkenes (Schemes 3–5). 広報資料 澤村 正也 １．論 文 (1) Phosphorus Ligands with a Large Cavity: Synthesis of Triethynylphosphines with Bulky End Caps and Application to the Rhodium-Catalyzed Hydrosilylation of Ketones. Ochida, A.; Sawamura, M. Chem. Asian J.2007, 2, 609–618. (2) Monocoordinating, Compact Phosphane Immobilized on Silica Surface: Application to Rhodium-Catalyzed Hydrosilylation of Hindered Ketones.Hamasaka, G.; Ochida, A.; Hara, K.; Sawamura, M Angew. Chem. Int. Ed.2007, 46, 5381–5383. (3) Conductance of Single 1,4-Disubstituted Benzene Molecules Anchored to Pt Electrodes. Kiguchi, M.; Miura, S.; Hara, K.; Sawamura, M.; Murakoshi, K. App. Phys. Lett. 2007, 91, 053110. (4) Enantioselective Addition of Terminal Alkynes to Aldehydes Catalyzed by a Cu(I)–TRAP Complex.Asano, Y.;Hara, K.;Ito, H.;Sawamura, M Org. Lett.2007, 9, 3901–3904. (5) Synthesis and Structural Characterization of Tetranuclear Platinum(II) Metallamacrocycle Containing 1,3-Diisocyanoarene Ligands. Ito, H.; Maeda, T.: Sawamura, M Bull. Chem. Soc. Jpn. 2007, 80, 1981–1986. (6) Functionalization of Silicon Surface with Catalytically Active Pd Complex and Application to the Aerobic Oxidation of Benzylic Alcohols.Hara, K.;Tayama, S.;Kano, H.;Masuda, T.;Takakusagi, S.;Kondo, T.;Uosaki, K.;Sawamura, M Chem. Commun. 2007,4280–4282. (7) Design and Synthesis of IsocyanideLigands for Catalysis:Application to Rh-catalyzed Hydrosilylation of Ketones.Ito, H.;Kato, T.;Sawamura, M Chem. Asian J.2007,2, 1436–1446. (8) Construction of Self-assembled Monolayer Terminated with N-Heterocyclic Carbene–Rhodium(I) Complex Moiety. Hara,K.;Iwahashi, K.;Takakusagi, S.;Uosaki, K.;Sawamura, M Surf. Sci.2007,601, 5127–5132. (9) Copper-Catalyzed Enantioselective Substitution of Allylic Carbonates with Diboron: An Efficient Route to Optically Active α-ChiralAllylboronates. Ito, H.;Ito, S. ; Sasaki, Y.;Matsuura, K.;Sawamura, M J. Am. Chem. Soc.2007, 129, 14856–14857. ２．講 演 (1) Ỉᱜ䋬 ⸅ᇦ⸳⸘䈮ᣂ䈚䈇ᔨ䉕᳞䉄䈩䋬 ⸅ᇦቇળർᶏᧅᏻ⻠Ṷળ䇮 ᯏ㊄ዻ⎇ⓥળ Organometallic Seminar XXXV 䇸㛽ᄥ䈱ᯏ㊄ዻ 䊶 ⸅ᇦൻቇ䇹䋬 ᧅᏻ䋬 2007 ᐕ 12 5 ᣣ䋬 ᓙ⻠Ṷ (2) Ỉᱜ 䇭Masaya Sawamura䋬 Silica-Supported Compact Phosphine and Its Use for Rh- and Ir-Catalysis䋬 China–Japan Joint Symposiumon Functional Materials toward Future Catalysts䋬 Peking, Chaina 2008 ᐕ 1 16 ᣣ䋬 ᓙ⻠Ṷ (3) Ỉᱜ䋬 ㊄㵩䊖䉴䊐䉞䊮㍲⸅ᇦ䈱ಽሶ⸳⸘䋬 Ꮊᄢቇℂቇᐭ㒮↢ડ↹䉲䊮䊘䉳䉡䊛䇭䌾㊄⸅ᇦ䈱ዷᦸ䌾䋬 ጟ䋬 2008 ᐕ 3 19 ᣣ䋬 ᓙ⻠Ṷ 学会・シンポジウム (1) China–Japan Joint Symposiumon Functional Materials toward Future Catalysts䋬 2008 ᐕ 1 16 ᣣ 䋬 Peking, China䋬 Coorganizer
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