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$Ver‡Š‹ïç«PðBCD5ñòó<›
œ••€ïç¨VôßL‡¡¢ 2 á¤
sõ<ÏÒ561¦¥âTP C 4Š‹ÔÕÖÏ?Vö˜
Ll™h÷5ãävøù<í„úûIƒ„<OPQRSTUPö˜B™rlÛÜZ{XYW
Ißàpq‡s
! Y<CüB5./0123<OPQRSTUPö˜B4Š‹ÔÕÖÏ?©ý6789øù
Iþÿ•@•lrXYWgh5YqhV‰žLÅ!fXYWZ5ÃkMN./0123<?
‰atç"±PV
•lrº‡rW#$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
!"#$%
¢1. PF1171F<j$•€ (£) WÏЕ€ (á)%
&Ñ4Š‹ÔÕÖÏ?Vßf%
¢2. 61¦¥âTP C <j$•€ (£) W
NMR žŸBCDôßpq‡•€ (á)%
!
! RNA !"#$%&'"()*+,-./0
12 3456789:;
! "#$%&'()*+,-, ./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.
© Copyright 2024 Paperzz
