Rh(II)!"#$%&'()*+,-./0123456789Diels–Alder :;<=>/?<;2 !"#$%$%&'%()&* +,* -.@ * /0 Rh(II)123456789:;<=>?@AB>CDEFGHIJKEL MENOPQR6SG;<=>SNTUGHIVWXYZ[\]^_`=Ca bJ7cd7EZAefZghijkCENKlYm`Vn:;okpYhq ^_`=Crst3JN-uvwNE-(S)-7OPlxy2;z{fZ|Ym`}~ •€• Rh(II)12V‚ƒ;9„YkC…†WXHI‡ˆ()V‰ŠYm`J Rh(II)12VENKlWXYm`V‹ŒnA•ŽmJc•E• Rh(II)12;<=> …†‘’w Diels–Alder (HDA)HIV‡ˆ;“”`•>rp_–—AJFG8uv ENO˜9;}~•€• Rh(II)7O™RT12 Rh2(S-BPTPI)4hJDanishefsky š 6›GY457Eœ•˜YV…† HDA HIAž=`JŸ `¡=…†¢£ž¤ ¥…†ENKlWXYm`3¦§VWX¨n;okpY;©ªm>1r Rh2(S-BPTPI)4;<=>…† HDA HI3«¬•›G˜-®n—¯“kC> J 2,3-dKf[V6•˜w°•PGV~h±CpYh—•Cr–>JRh2(S-BPTPI)4 3²V…†ENKlWXV³<h´µ• Rawal 6›Gž¤¥2-7¶-3-d·E¸ cd-1,3-¹v6›G(Ghosez 6›G)Y7Eœ•˜YV…† HDA HIAº»¼— ½CpYh¾b”>2,3r¿ÀÁ—3p_–—VÂÞ¤¥¿HI;ÄÅYkC? [Æ°•GÇÈ;ºÉÊ˨nÌÍËVWXÎ…†ÏÐAÉ=`ÑÒm>=r 1. (a) Anada, M.; Washio, T.; Shimada, N.; Kitagaki, S,; Nakajima, M.; Shiro, M.; Hashimoto, S. Angew. Chem. Int. Ed. 2004, 43, 2665. (b) Anada, M.; Washio, T.; Watanabe, Y.; Takeda, K.; Hashimoto, S. Eur. J. Org. Chem. 2010, 6850. 2. (a) Watanabe, Y.; Washio, T.; Shimada, N.; Anada, M.; Hashimoto, S. Chem. Commum. 2009, 7294. (b) Watanabe, Y.; Shimada, N.; Anada, M.; Hashimoto, S. Tetrahedron: Asymmetry 2014, 25, 63. 3. Watanabe, Y.; Washio, T.; Krishnamurthi, J.; Anada, M.; Hashimoto, S. Chem. Commum. 2012, 48, 6969. !"#$%&'()*+,-./012345678 8 /9:;<8 =>3?@ !"#ABCDAEFG8 H?I8 JCKAEFL8 012! "#!$%&'()*+! ! "#$%&'()*+,-./'()0+1-2345+6&789:;<=>?@ AOSUBCDEFGH I@J Rich G. Carter KLMNOPKQAR@BSTUVW XY3Z/[VKL(\S]^_`abD3cdefW ! ! g<hiFj A (1) %&OSU 4 K. L. McPhail /kl 26 mnFop4Oqrst./uvwxyz{|V}~•3 18 H €•&‚kƒ„… NCI-H460 †‡ˆg‰GŠ‹Œ„…• 17 OH 20 O 15 H Neuro-2A NŽ|•b•‘’:“’4”•–„…—rS ˜|•™f OH O O 1 [IC50 = 12 nM (NCI-H460), 44 nM 12 11 H (Neuro-2A)].1) xyš–›œ•|•%&cis žŸ|V THF (C17-C20) †‡ˆ THPAC5-C9BŸS 23 21 O 9 ¡¢£¤N˜ef H 5 7 6' O 24 ¥g¦§i¦¨<Ÿxy3€fY•k©ª/[fW 1' ! «¬%&Y[/4-@®r– cis -THF †‡ˆ THP Ÿ HO O H O H OH Sx¯efV°N&“<±²D¨S˜ef³§´’µ’m マンデラリド A (1) ’CD’ 2 †‡ˆs‘³§´’µ’m’CD’ 4 S¶ ™V·(I) ¸¹N‡fŸIº»S¼½¾•|•&¿À cis-2,5-ÁÂj§ni< (DHF) Ÿ 3 †‡ˆ 3,6-ÁÂj§Ãi< (DHP) Ÿ 5 SX[Ä[Å(efY•N(Æ|V4 3&Y[/4‘h’ÇÈSÉ°VÅ(KL4Ê„SËÌÍΕ™VÏÐW OH 20 17 R1 R1 OH 18 2 9 5 7 20 O H R2 OH 2,5-DHF 3 H OBz R3 17 H OBz OH OBz 18 AgCC R2 AgCC R4 R3 O 9 H 5 R4 7 OBz 4 3,6-DHP 5 AgCC = Ag(I)-Catalyzed Cyclization DHF = dihydrofuran, DHP = dihydropyran References 1) a) Sikorska, J.; Hau, A. M.; Anklin, C.; Parker-Nance, S.; Davis-Coleman, M. T.; Ishmael, J. E.; McPhail, K. L. J. Org. Chem. 2012, 77, 6066-6075. b) Correction: J. Org. Chem. 2013, 78, 2812. !"#$%&'()*+,-./012345! !"#$#$%&$'()! *+ ,./0123456789:;<=>?@ABCDEF<GHIJKL5MNOPQRS TUPVWXYWZ[P\]^W_`aBbcdefXYWgh5i&<TS3j?kWL lmnopqlrXsLgLtIh5./01234uv<wxIyzZ{XI|B5}~ •€<•‚BCDƒ„<OPQRSTUPI•@X…†NI{X‡ˆ5?‰atŠ‹Œ•I Ž•Z{•‡s‘’“”45./0123<j$•€WOPQRSTUP<•–V—hgB fXYWVoaWLl5./0123<?˜™Cš›œ••€žŸV •lrXs PF1171F¡¢ 1 £¤456P¥¦§¨9©ª0O«P9t¬<_-t6789V®¯fX. /0123Z{D5°±OB²Ll³´µ¶Z·¸V¹º»YL5¼¥½¾¿ÀZ46Á« Á[P\]^ B <ÂÃVÄÅfXs‘’“”45ÆbZ<0123vÇÈWÉbZ<Ê]Ë ¦][ÌjBCD5PF1171F <ƒ?˜V •‡sÍhq‡ÎÏÐ< X ÑÏЕ€žŸV • ‡ÏÒ54 Ó<Š‹ÔÕÖÏ?<JKI×Øpq5YqhIOPQRSTUP<ÙÚBÛÜ tÝÞVÒ‡LlrXYWIßàpq‡¡¢ 1 á¤s 61¦¥âTP C¡¢ 2 £¤450123vBãäv©26å«PIæÏL‡./ç1T 0123Z{D5_è<é¿ÀêB²LlërìNVßfs‘’“”4561¦¥âTP C V?˜L5NMR BCXí„•€žŸW•îj$Ver‡Š‹ïç«PðBCD5ñòó<› œ••€ïç¨VôßL‡¡¢ 2 ᤠsõ<ÏÒ561¦¥âTP C 4Š‹ÔÕÖÏ?Vö˜ Ll™h÷5ãävøù<í„úûIƒ„<OPQRSTUPö˜B™rlÛÜZ{XYW Ißàpq‡s ! Y<CüB5./0123<OPQRSTUPö˜B4Š‹ÔÕÖÏ?©ý6789øù Iþÿ•@•lrXYWgh5YqhV‰žLÅ!fXYWZ5ÃkMN./0123<? ‰atç"±PV •lrº‡rW#$lrXs ! MeO O N H HN N N O Me N HN O H N HN O O O Ph O S N O Me N O N O O HO O !"#$% ¢1. 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"#$%&'()*+,-, ./0123./0456789:;<=>?@ABCDE*FGH>I<JK LMN(OPQRPOPSTUVWPXYN(ZPG[\]<^H*ON_*`abA"#$%&'()cde ]fSgMhi- 1 jk / 2 jk DNA *lmnoMpi-I<qr*sDtuvwx9yHJz{M|}~M •€*"#$%&'()- DNA / RNA •*$%vwx~‚ƒ„MRNA ~…ƒf†‡Avwx9,Kˆ<* -M‰Š‹ŒGƒf•Ž•]<•‘’V&“”)•–%‹~—˜™e]fš<J ! |›Mœie-MDNA ^?k•*žsDŸ (AP site) ~¡¢b~$%ƒ£<¤¥0&'()9¦§ƒM¨ ]9•Žƒ{ DNA (|sD©a6ª&«¬R-®)&¯Pª) °§±3•²³´µ³P¶·W–±*+,9¸¹ fº{[1]Jz{M¦§ƒ{&'()- RNA ^?k•* AP site ~»$%ˆ<¨Gc>ºM|Ÿ*&'()c RNA ^?k~…ƒf¼ƒš$%vwx9,Kƒ£<¨G9¦§ƒfš<[2]JA½>»¾•‘’¯¶¾(¿ÀÁ •‘öN)Ä*$%¡x-Å]{»*>[2a]M|jk RNA 3ÆÇÈÉ RNA ^?kG-$%ÊËMAP site Ì Í RNA ^?kG¡¢b~$%ƒMRNA ^?kG*$%ÎÏÐÂ1ÑÒÓ Kd = 9.5 nMÄ-MDNA ^?k (Kd = 740 nM) GÔÕƒf^Ö×؃{J¨]-MRNA ^?kc¯Ù®•Ú*Ûš A aÜÝ9G<{¹MB aÜÝ9 G< DNA ^?kGÔÞfßàsDG*áOÙâ(VcTgãäb~åæˆ<{¹Gç;e]M$%èéWêP *ëÐìb12*$仨]9:yƒfš<J•e~MíLtuÂlet-7 ²î‘&PÄ9…ïGƒf•‘öN) 9 microRNAÂmiRNAÄ°§ðñŽƒ{$äM1.2 nMÂ59 fmol in 50 µLÄ*òó°§côo>õ•€*’Pö( XÃÙµ³(V±G—˜÷qr*°§ør9̓fš<¨Gcù½ú{J ! KLMmiRNA *126Òû-õPCR ±9üÁGˆ<•€* DNA 12BC9ýŽˆ<¨G>þù]fš<cM sDÿcÛš{¹M!*zzPCR ×"~#ˆ<¨Gc>ºAšGšú{jŒbA$%9&;fš<J¨¨>' e]{$ä-MmiRNA °§~"#$%&'()*•Žcãäb>I<¨G9()ˆ<»*>M*p•e~&' ()*+,9¸¹<¨G>M PCR ×"9-@Gˆ<miRNA ~¡–ƒ{°§±~Ag£<G./>º<J ! z{Mœie-MRNA *YW¾ÜÝ90bGˆ<12x&'()*+,~34ƒM¨]z>~&56P7 RNA * A-site ~$%ƒ£<¤¥0&'()9¦§ˆ¨G~89ƒfš<J:Áb~-M;²®&¾(<= Â2-amino-5,6,7-trimethyl-1,8-naphthyridineÄ~•‘’è®WD9>$ƒ{»*>M•‘’V&“”)¿ÀÁÂex. ribostamycin, Kd = 0.31 µMÄ~?@ˆ<$%ÎÏÐ9,Kˆ<¨GÂKd = 0.53 µMÄ Mz{MA•‘’V&“”)• * A-site $%&'()GƒfBCR·W*$%Ð>I<¨Gcù½ú{J ! RNA ~€Lˆ<YW¾ÜÝ-MRNA *DEÜÝ~FGƒM©HAŠ‹ìb_ÃIá~Jùúfš<JA½> »M&56P7RNA * A-site -M!*ÜÝGno*ÈJc†e½~•]fš<KLbAYW¾ÜÝ*|H>M MNÂOPNÄ+,*ü@AOPQÙª*|HGAúfš<JKLM•‘’V&“”)¿ÀÁcDÎÏx* A-site $%&'()Gƒfde]fš<cMA•‘’V&“”)•*$%&'()9+,ˆ<¨G>MOPN+,~S R<Sƒš¥0TUVW9X#ƒ£<¨Gc./>º<Jz{M12x&'()9+,ˆ<¨G>MOPN+, 9:Yˆ<Z[M\]½H^_Aá¬&P´(V±*+,~HAc<»*Gç;fš<J ! `œ>-M¨]e*ab8ä~Hšfcd•Êfš{eº{šJ (1) (a) Chem. Eur. J., 2011, 17, 11650–11656. (b) Chem. Commun., 2011, 47, 5885–5887. (c) Chem. Eur. J., 2011, 17, 14104–14110. (d) Biosens. Bioelectron., 2011, 26, 4733–4738. (e) ChemBioChem, 2012, 13, 436–442. (f) Chem. Eur. J., 2012, 18, 9481–9484. (g) Chem. Eur. J., 2012, 18, 12719–12724. (h) Chem. Eur. J., 2013, 19, 10526–10535. (2) (a) Angew. Chem. Int. Ed., 2012, 51, 6369-6372. (b) Chem. Commun., 2013, 49, 9983–9985. (c) Chem. Commun., 2014, 50, 515–517.
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