{"id":49212,"date":"2024-03-14T08:00:48","date_gmt":"2024-03-14T00:00:48","guid":{"rendered":"\/\/www.gsbet888.com\/?p=49212"},"modified":"2024-03-13T16:53:34","modified_gmt":"2024-03-13T08:53:34","slug":"jacs%ef%bc%9a%e5%a4%a9%e7%84%b6%e4%ba%a7%e7%89%a9-hunterine-a%e7%9a%84%e5%85%a8%e5%90%88%e6%88%90","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2024\/03\/jacs%ef%bc%9a%e5%a4%a9%e7%84%b6%e4%ba%a7%e7%89%a9-hunterine-a%e7%9a%84%e5%85%a8%e5%90%88%e6%88%90.html","title":{"rendered":"JACS\uff1a\u5929\u7136\u4ea7\u7269(+)-Hunterine A\u7684\u5168\u5408\u6210"},"content":{"rendered":"

\u4f5c\u8005\uff1a\u77f3\u6cb9\u919a<\/strong><\/p>\n

\u5bfc\u8bfb\uff1a<\/h4>\n
\u8fd1\u65e5\uff0c California Institute of\u00a0 Technology\u7684Brian M. Stoltz\u56e2\u961f\u5728J. Am. Chem. Soc.<\/em>\u4e0a\uff0c\u4ee5 \u201cEnantioselective Total Synthesis of (\u2212)-Hunterine A Enabled by a Desymmetrization\/Rearrangement Strategy\u201d \u4e3a\u9898\uff0c\u9996\u6b21\u62a5\u9053\u4e86\u5929\u7136\u4ea7\u7269(\u2212)-Hunterine A\u5bf9\u6620\u9009\u62e9\u6027\u5168\u5408\u6210\u3002\u5176\u4e2d\u5173\u952e\u6b65\u9aa4\u6d89\u53ca1\uff09\u5bf9\u79f0\u4e8c\u916e\u7684\u7684\u4e0d\u5bf9\u79f0\u50ac\u5316\u53bb\u5bf9\u79f0\u5316(catalytic asymmetric desymmetrization of a symmetrical diketone)\u3001Beckmann\u91cd\u6392\u6765\u6784\u5efa5,6-\u03b1-\u6c28\u57fa\u916e(Beckmann rearrangement to construct a 5,6-\u03b1-aminoketone)\u3001\u4e59\u70ef\u57fa\u4eb2\u6838\u8bd5\u5242\u548c\u624b\u6027\u916e\u76841,2-\u52a0\u6210(1,2-addition joins a vinyl dianion nucleophile and the enantioenriched ketone)\u3001\u6c2e\u6742-Cope\/ Mannich\u53cd\u5e94(aza-Cope\/Mannich reaction)\u548c \u53e0\u6c2e\u5316\u7269-\u70ef\u70c3\u7684\u5076\u6781\u73af\u52a0\u6210(azide-olefin dipolar cycloaddition) \u6784\u5efa\u4e94\u5143\u73af<\/p>\n
\u201cEnantioselective Total Synthesis of (\u2212)-Hunterine A Enabled by a Desymmetrization\/Rearrangement Strategy.<\/p>\n
Elliot F. Hicks, Kengo Inoue, and Brian M. Stoltz<\/p>\n
J. Am. Chem. Soc.<\/em>, 2024, <\/strong>ASAP<\/em>. doi: <\/a>10.1021\/jacs.3c13590\u201d<\/p><\/blockquote>\n
\u6b63\u6587<\/h4>\n
\u5355\u841c\u5432\u54da\u751f\u7269\u78b1(Monoterpene indole alkaloids\uff0cMIAs)\u662f\u4e00\u7c7b\u7ed3\u6784\u591a\u6837\u7684\u5929\u7136\u4ea7\u7269\u3002\u7531\u4e8e\u5176\u590d\u6742\u591a\u6837\u7684\u751f\u7269\u6d3b\u6027\uff0c\u51e0\u5341\u5e74\u6765\u4e00\u76f4\u53d7\u5230\u5408\u6210\u5316\u5b66\u5bb6\u5e7f\u6cdb\u7684\u5173\u6ce8^{[1]<\/sup>\u3002\u8be5\u5bb6\u65cf\u5206\u5b50\u9aa8\u901a\u5e38\u4ee5\u4e0e\u5404\u79cd\u91cd\u6392\u841c\u70ef\u5355\u5143\u7ed3\u5408\u7684\u5432\u54da\u6216\u5432\u54da\u5549\u7247\u6bb5\u4e3a\u7279\u5f81(Figure 1)\u3002\u7136\u800c\uff0c\u5df2\u7ecf\u5206\u79bb\u542b\u6709\u5c11\u91cf\u542b\u6709\u91cd\u6392\u7684\u5432\u54da\u5355\u5143\u7684MIAs\uff0c\u5176\u4e2dC2-C7\u952e\u53d1\u751f\u65ad\u88c2^{[2] <\/sup>(\u78b3\u7f16\u53f7\u9075\u5faa\u5206\u5b50\u5206\u79bb\u65f6\u7ed9\u51fa\u7684\u7f16\u53f7)\u3002\u76ee\u524d\uff0c\u79d1\u5b66\u5bb6\u5df2\u7ecf\u5229\u7528\u4f18\u96c5\u7684\u5168\u5408\u6210\u65b9\u6cd5\u5b8c\u6210\u4e86MIA\u5bb6\u65cf\u6210\u5458\u4e2d\u8bb8\u591a\u5206\u5b50\u7684\u5168\u5408\u6210\uff0c\u5305\u62ec\u90a3\u4e9b\u542b\u6709C2-C7\u5432\u54da\u65ad\u88c2\u7684\u65b9\u6cd5\u6cd5\u3002<\/p>\n}}
\u5929\u7136\u4ea7\u7269(\u2212)-Hunterine A(1<\/strong>)\u662f\u7531\u4e2d\u56fd\u79d1\u5b66\u5bb6\u5f20\u6653\u7426\u6559\u6388^{[3]<\/sup>\u53ca\u5176\u540c\u4e8b\u4e8e2019\u5e74\u4eceHunteria Zeylanica\u4e2d\u5206\u79bb\u83b7\u5f97[3] (Figure 1)\uff0c\u5176\u5c5e\u4e8e\u4e00\u7c7b\u7ed3\u6784\u72ec\u7279\u7684\u5355\u5e16\u5432\u54da\u751f\u7269\u78b1\uff0c\u5176\u4e2dN1-C2\u7684\u5432\u54da\u952e\u53d1\u751f\u65ad\u88c2(Figure 1)\u3002\u9664\u6b64\u4e4b\u5916\uff0c\u8be5\u5206\u5b50\u5bf9HepG2\u809d\u764c\u7ec6\u80de\u7cfb(35 \u03bcM)\u5177\u6709\u4e2d\u7b49\u7684\u7ec6\u80de\u6bd2\u6d3b\u6027\u3002\u8fc4\u4eca\u4e3a\u6b62\uff0c\u4ec5\u5206\u79bb\u51fa\u4e00\u79cd\u7ed3\u6784\u76f8\u5173\u7684\u5929\u7136\u4ea7\u7269\uff0c\u5e76\u4e14\u6ca1\u6709\u5408\u6210\u8fd9\u4e24\u79cd\u751f\u7269\u78b1\u7684\u62a5\u9053\u3002\u8fd1\u65e5\uff0cCalifornia Institute of\u00a0 Technology\u7684Brian M. Stoltz\u6559\u6388\uff0c\u9996\u6b21\u62a5\u9053\u4e86\u5929\u7136\u4ea7\u7269(\u2212)-Hunterine A\u5bf9\u6620\u9009\u62e9\u6027\u5168\u5408\u6210\uff0c\u5e76\u53d1\u8868\u4e8eJ. Am. Chem. Soc.<\/em>\u4e0a\u3002<\/p>\n}
$\"\"$ \u00a0(\u2212)-Hunterine A(1<\/strong>)\u542b\u6709\u6865\u8054\u6c2e\u6742\u53cc\u73af[4.3.1]\u7678\u70f7\u6838\u5fc3\u9aa8\u67b6\uff0c\u5e76\u4e14\u8fd8\u5177\u6709N1\u548cC18\u9187\u7684\u4e0d\u548c\u8c10\u6c27\u5316\u6a21\u5f0f(dissonant oxidation pattern)\u4ee5\u53caC19\u7acb\u4f53\u5316\u5b66\u7b49\u7279\u70b9\u3002 \u57fa\u4e8e\u5176\u7279\u6b8a\u7684\u9aa8\u67b6\uff0c\u4f5c\u8005\u5bf9(\u2212)-Hunterine A(1<\/strong>)\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u9006\u5408\u6210\u5206\u6790(Scheme 1A)\uff0c\u5373\u5bf9\u79f0\u4e8c\u916e6<\/strong>\u7ecf\u53bb\u5bf9\u79f0\u5316\u548c\u91cd\u6392\u6765\u6784\u5efa\u780c\u57575\uff0c4<\/strong>\u548c5<\/strong>\u901a\u8fc7\u6c47\u805a\u5f0f\u548c\u975e\u5bf9\u6620\u9009\u62e9\u60271,2-\u52a0\u6210\u53cd\u5e94\u5236\u5907\u780c\u57573<\/strong>\u3002\u968f\u540e\uff0c<\/strong>3<\/strong>\u7ecfaza-Cope\/Mannich \u91cd\u6392\u53cd\u5e94\u83b7\u5f97\u4e2d\u95f4\u4f532\u3002<\/strong>\u6700\u540e\uff0c2<\/strong>\u7ecf\u8fc7\u540e\u671f\u5b98\u80fd\u56e2\u4fee\u9970\u5b8c\u6210\u5929\u7136\u4ea7\u7269(\u2212)-Hunterine A(1<\/strong>)\u7684\u5168\u5408\u6210\u3002\u57fa\u4e8e1<\/strong>\u4e2d\u4e0d\u542b\u5432\u54da\uff0cC7\u5168\u78b3\u56db\u5143\u4e2d\u5fc3\u4e0d\u53ef\u4f7f\u7528\u5176\u4ed6\u76f8\u5173MIAs\u7684\u5408\u6210\u7b56\u7565\uff0c\u540e\u8005\u901a\u5e38\u91c7\u7528Fischer\u5432\u54da\u5408\u6210\u548c\u4eb2\u6838\u5432\u54da\u70f7\u57fa\u5316(\u65b9\u68481B)\u7b49\u7b56\u7565\u3002 $\"\"$ <\/p>\n
\u9996\u5148\uff0c\u4f5c\u8005\u4ee5\u4e0d\u5bf9\u79f0\u6c22\u5316\u5bf9\u5bf9\u79f0\u4e8c\u916e6<\/strong>\u7684\u53bb\u5bf9\u79f0\u5316\u8fdb\u884c\u4e86\u7b5b\u9009\uff0c\u5982Table 1\u6240\u793a\u3002\u5373\u5bf9 Noyori \u7684\u8f6c\u79fb\u6c22\u5316\u6761\u4ef6\u8fdb\u884c\u6539\u826f^{[4]<\/sup>\uff0c\u4ee5 RuCl(mesitylene)(R,R-TsDPEN) \u4f5c\u4e3a\u50ac\u5316\u5242\uff0c\u5728(5:2) \u7532\u9178\/\u4e09\u4e59\u80fa\u6df7\u5408\u7269\u5b9e\u73b0\u4e86\u5bf9\u79f0\u4e8c\u916e6<\/strong>\u7684\u53bb\u5bf9\u79f0\u5316\uff0c\u5e76\u4e14\u5185\u6d88\u65cb\u4e8c\u918711<\/strong>\u5bf9\u53cd\u5e94\u6709\u660e\u663e\u7684\u624b\u6027\u62c6\u5206\uff0c\u8fdb\u800c\u63d0\u9ad810<\/strong>\u7684\u5bf9\u6620\u4f53\u7eaf\u5ea6\u3002<\/p>\n}
$\"\"$ <\/p>\n
\u53e6\u5916\u4e00\u65b9\u9762\uff0c\u4f5c\u8005\u5bf9aza-Cope\/Mannich \u53cd\u5e94\u8fdb\u884c\u4e86\u5c1d\u8bd5\uff0c\u5982\u56feScheme 3\uff0c\u5373\u7528AgNO_{3<\/sub>\u5904\u7406aniline 18 <\/strong>\u53d1\u751faza-Cope\/Mannich \u53cd\u5e94^{[5]<\/sup>\u5f62\u6210\u5432\u54da\u4e9a\u80fa 23<\/strong>\uff0c23<\/strong>\u7528 NaBH_{4 <\/sub>\u5904\u7406\uff0c<\/strong>\u7136\u540ePd\/C\u8fd8\u539f\u53cc\u952e\uff0c\u4e09\u6b65\u5b8c\u6210\u4e86(\u2212)-aspidospermidine\u7684\u5408\u6210\u3002<\/p>\n}}}
$\"\"$ <\/p>\n
\u5929\u7136\u4ea7\u7269(\u2212)-Hunterine A(1<\/strong>)\u7684\u5168\u5408\u6210\u6b65\u9aa4\uff0c\u5982Scheme 2\u6240\u793a\u3002<\/p>\n
$\"\"$ $\"\"$ <\/p>\n
\u6700\u540e\uff0c\u4f5c\u8005\u5bf9C19-epi-20<\/strong>\u548c20<\/strong>\u4e2d\u7684\u4e09\u6c2e\u5511\u5149\u89e3\u4f5c\u7528\u83b7\u5f97\u4e0d\u540c\u7684\u53cd\u5e94\u6027\uff0c\u5982Scheme 4\u6240\u793a\u3002\u5373\u4ee5\u82ef\u4e3a\u6eb6\u5242\uff0c\u7528\u4e59\u9178\u5904\u7406\u4e09\u5511\u5549 20 <\/strong>\u6210\u529f\u751f\u6210\u4e86 O-\u4e59\u9170\u57fa-hunterine A\uff0c\u800c\u7528\u4e59\u9178\u5904\u7406C19-epi-20<\/strong>\u901a\u8fc7\u4e2d\u95f4\u4f5325<\/strong>\u4ee555%\u7684\u6536\u7387\u5f62\u6210\u4e9a\u80fa26<\/strong>\uff0c\u5e76\u6ca1\u6709\u751f\u6210C19-O-\u4e59\u9170\u57fa-hunterine A\u7684\u5dee\u5411\u5f02\u6784\u4f53\u3002\u7efc\u4e0a\uff0c\u4f5c\u8005\u63a8\u6d4b\u53cd\u5e94\u6027\u5dee\u5f02\u4e0e\u5404\u4e2a\u6c2e\u539f\u5b50\u5728\u7a7a\u95f4\u7684\u7ed3\u6784\u6709\u5173\uff0c\u5373\u9525\u5ea6\u7684\u5c5e\u6027\u300220<\/strong>\u6676\u4f53\u7ed3\u6784\u4e2d\u76f8\u5173\u952e\u89d2\u7684\u603b\u548c\u8868\u660e\u6c2e\u539f\u5b50\u4e3a45%\u9525\u4f53^{[6]<\/sup>\uff0c\u800c\u5728C19-epi-20<\/strong>\u4e2d\uff0c\u6c2e\u539f\u5b50\u4ec5\u4e3a9%\u9525\u4f53\u3002<\/p>\n}
$\"\"$ <\/p>\n
\u603b\u7ed3\uff0cBrian M. Stoltz\u56e2\u961f\u5728J. Am. Chem. Soc.<\/em>\u4e0a\uff0c\u4ee5 \u201cEnantioselective Total Synthesis of (\u2212)-Hunterine A Enabled by a Desymmetrization\/Rearrangement Strategy\u201d \u4e3a\u9898\uff0c\u9996\u6b21\u62a5\u9053\u4e86\u5929\u7136\u4ea7\u7269(\u2212)-Hunterine A\u5bf9\u6620\u9009\u62e9\u6027\u5168\u5408\u6210\u3002\u5176\u4e2d\u5173\u952e\u6b65\u9aa4\u6d89\u53ca1\uff09\u5bf9\u79f0\u4e8c\u916e\u7684\u7684\u4e0d\u5bf9\u79f0\u50ac\u5316\u53bb\u5bf9\u79f0\u5316(catalytic asymmetric desymmetrization of a symmetrical diketone)\u3001Beckmann\u91cd\u6392\u6765\u6784\u5efa5,6-\u03b1-\u6c28\u57fa\u916e(Beckmann rearrangement to construct a 5,6-\u03b1-aminoketone)\u3001\u4e59\u70ef\u57fa\u4eb2\u6838\u8bd5\u5242\u548c\u624b\u6027\u916e\u76841,2-\u52a0\u6210(1,2-addition joins a vinyl dianion nucleophile and the enantioenriched ketone)\u3001\u6c2e\u6742-Cope\/ Mannich\u53cd\u5e94(aza-Cope\/Mannich reaction)\u548c \u53e0\u6c2e\u5316\u7269-\u70ef\u70c3\u7684\u5076\u6781\u73af\u52a0\u6210(azide-olefin dipolar cycloaddition) \u6784\u5efa\u4e94\u5143\u73af<\/p>\n
\u53c2\u8003\u6587\u732e:<\/h4>\n\n
[1]\u00a0\u00a0 S. E. O’Connor, J. J. Maresh, Nat. Prod. Rep. <\/em>2006<\/strong>, 23<\/em>, 532. doi:**10.1039\/B512615K.<\/a><\/li>\n*
[2]\u00a0\u00a0 J.-J. Yao, R. Ding, X. Chen, H. Zhai, J. Am. Chem. Soc. <\/em>2022<\/strong>, *144<\/em>, 14396. doi:**10.1021\/jacs.2c06518.<\/a><\/li>\n*
[3]\u00a0\u00a0 J. Zhang, Z.-W. Liu, Y.-L. Ao, L.-J. Hu, C.-J. Wei, Q.-H. Zhang, M.-F. Yuan, Y. Wang, Q.-W. Zhang, W.-C. Ye, X.-Q. Zhang, The Journal of Organic Chemistry <\/em>2019<\/strong>, *84<\/em>, 14892. doi:**10.1021\/acs.joc.9b01835.<\/a><\/li>\n*
[4]\u00a0\u00a0 A. Fujii, S. Hashiguchi, N. Uematsu, T. Ikariya, R. Noyori, J. Am. Chem. Soc. <\/em>1996<\/strong>, *118<\/em>, 2521. doi:**10.1021\/ja954126l.<\/a><\/li>\n*
[5]\u00a0\u00a0 T. B. Dunn, J. M. Ellis, C. C. Kofink, J. R. Manning, L. E. Overman, Org. Lett. <\/em>2009<\/strong>, *11<\/em>, 5658. doi:**10.1021\/ol902373m.<\/a><\/li>\n*
[6]\u00a0\u00a0 K. L. Brown, L. Damm, J. D. Dunitz, A. Eschenmoser, R. Hobi, C. Kratky, Helv. Chim. Acta<\/em>\u00a0 1978<\/strong>, 61<\/em>, 3108. doi:10.1002\/hlca.19780610839<\/a>.<\/li>\n<\/ul>\n
\u672c\u6587\u7248\u6743\u5c5e\u4e8e\u00a0Chem-Station\u5316\u5b66\u7a7a\u95f4\uff0c \u6b22\u8fce\u70b9\u51fb\u6309\u94ae\u5206\u4eab\uff0c\u672a\u7ecf\u8bb8\u53ef\uff0c\u8c22\u7edd\u8f6c\u8f7d.<\/p>\n
\n","protected":false},"excerpt":{"rendered":"\u4f5c\u8005\uff1a\u77f3\u6cb9\u919a \u5bfc\u8bfb\uff1a \u8fd1\u65e5\uff0c California Institute of\u00a0 Technology\u7684Brian M. Stoltz\u56e2\u961f\u5728J. Am. Chem. Soc.\u4e0a\uff0c\u4ee5 \u201cEnantioselective Total Synthesis of (\u2212)-Hunterine A Enabled by a Desymmetrization\/Rearrangement Strategy\u201d \u4e3a\u9898\uff0c\u9996\u6b21\u62a5\u9053\u4e86\u5929\u7136\u4ea7\u7269(\u2212)-Hunterine A\u5bf9\u6620\u9009\u62e9\u6027\u5168\u5408\u6210\u3002\u5176\u4e2d\u5173\u952e\u6b65\u9aa4\u6d89\u53ca1\uff09\u5bf9\u79f0\u4e8c\u916e\u7684\u7684\u4e0d\u5bf9\u79f0\u50ac\u5316\u53bb\u5bf9\u79f0\u5316(catalytic asymmetric desymmetrization of a symmetrical diketone)\u3001Beckmann\u91cd\u6392\u6765\u6784\u5efa5,6-\u03b1-\u6c28\u57fa\u916e(Beckmann rearrangement to construct a 5,6-\u03b1-aminoketone)\u3001\u4e59\u70ef\u57fa\u4eb2\u6838\u8bd5\u5242\u548c\u624b\u6027\u916e\u76841,2-\u52a0\u6210(1,2-addition joins a vinyl dianion nucleophile and the enantioenriched ketone)\u3001\u6c2e\u6742-Cope\/ Mannich\u53cd\u5e94(aza-Cope\/Mannich reaction)\u548c \u53e0\u6c2e\u5316\u7269-\u70ef\u70c3\u7684\u5076\u6781\u73af\u52a0\u6210(azide-olefin dipolar cycloaddition) \u6784\u5efa\u4e94\u5143\u73af \u201cEnantioselective Total Synthesis of (\u2212)-Hunterine A Enabled by a Desymmetrization\/Rearrangement Strategy. Elliot F. Hicks, Kengo Inoue, and Brian M. Stoltz* J. Am. Chem. Soc., 2024, ASAP. doi: 10.1021\/jacs.3c13590\u201d \u6b63\u6587 \u5355\u841c\u5432\u54da\u751f\u7269\u78b1(Monoterpene indole alkaloids\uff0cMIAs)\u662f\u4e00\u7c7b\u7ed3\u6784\u591a\u6837\u7684\u5929\u7136\u4ea7\u7269\u3002\u7531\u4e8e\u5176\u590d\u6742\u591a\u6837\u7684\u751f\u7269\u6d3b\u6027\uff0c\u51e0\u5341\u5e74\u6765\u4e00\u76f4\u53d7\u5230\u5408\u6210\u5316\u5b66\u5bb6\u5e7f\u6cdb\u7684\u5173\u6ce8[1]\u3002\u8be5\u5bb6\u65cf\u5206\u5b50\u9aa8\u901a\u5e38\u4ee5\u4e0e\u5404\u79cd\u91cd\u6392\u841c\u70ef\u5355\u5143\u7ed3\u5408\u7684\u5432\u54da\u6216\u5432\u54da\u5549\u7247\u6bb5\u4e3a\u7279\u5f81(Figure 1)\u3002\u7136\u800c\uff0c\u5df2\u7ecf\u5206\u79bb\u542b\u6709\u5c11\u91cf\u542b\u6709\u91cd\u6392\u7684\u5432\u54da\u5355\u5143\u7684MIAs\uff0c\u5176\u4e2dC2-C7\u952e\u53d1\u751f\u65ad\u88c2[2] (\u78b3\u7f16\u53f7\u9075\u5faa\u5206\u5b50\u5206\u79bb\u65f6\u7ed9\u51fa\u7684\u7f16\u53f7)\u3002\u76ee\u524d\uff0c\u79d1\u5b66\u5bb6\u5df2\u7ecf\u5229\u7528\u4f18\u96c5\u7684\u5168\u5408\u6210\u65b9\u6cd5\u5b8c\u6210\u4e86MIA\u5bb6\u65cf\u6210\u5458\u4e2d\u8bb8\u591a\u5206\u5b50\u7684\u5168\u5408\u6210\uff0c\u5305\u62ec\u90a3\u4e9b\u542b\u6709C2-C7\u5432\u54da\u65ad\u88c2\u7684\u65b9\u6cd5\u6cd5\u3002 \u5929\u7136\u4ea7\u7269(\u2212)-Hunterine A(1)\u662f\u7531\u4e2d\u56fd\u79d1\u5b66\u5bb6\u5f20\u6653\u7426\u6559\u6388[3]\u53ca\u5176\u540c\u4e8b\u4e8e2019\u5e74\u4eceHunteria Zeylanica\u4e2d\u5206\u79bb\u83b7\u5f97[3] (Figure 1)\uff0c\u5176\u5c5e\u4e8e\u4e00\u7c7b\u7ed3\u6784\u72ec\u7279\u7684\u5355\u5e16\u5432\u54da\u751f\u7269\u78b1\uff0c\u5176\u4e2dN1-C2\u7684\u5432\u54da\u952e\u53d1\u751f\u65ad\u88c2(Figure 1)\u3002\u9664\u6b64\u4e4b\u5916\uff0c\u8be5\u5206\u5b50\u5bf9HepG2\u809d\u764c\u7ec6\u80de\u7cfb(35 \u03bcM)\u5177\u6709\u4e2d\u7b49\u7684\u7ec6\u80de\u6bd2\u6d3b\u6027\u3002\u8fc4\u4eca\u4e3a\u6b62\uff0c\u4ec5\u5206\u79bb\u51fa\u4e00\u79cd\u7ed3\u6784\u76f8\u5173\u7684\u5929\u7136\u4ea7\u7269\uff0c\u5e76\u4e14\u6ca1\u6709\u5408\u6210\u8fd9\u4e24\u79cd\u751f\u7269\u78b1\u7684\u62a5\u9053\u3002\u8fd1\u65e5\uff0cCalifornia Institute of\u00a0 Technology\u7684Brian M. Stoltz\u6559\u6388\uff0c\u9996\u6b21\u62a5\u9053\u4e86\u5929\u7136\u4ea7\u7269(\u2212)-Hunterine A\u5bf9\u6620\u9009\u62e9\u6027\u5168\u5408\u6210\uff0c\u5e76\u53d1\u8868\u4e8eJ. Am. Chem. Soc.\u4e0a\u3002 \u00a0(\u2212)-Hunterine A(1)\u542b\u6709\u6865\u8054\u6c2e\u6742\u53cc\u73af[4.3.1]\u7678\u70f7\u6838\u5fc3\u9aa8\u67b6\uff0c\u5e76\u4e14\u8fd8\u5177\u6709N1\u548cC18\u9187\u7684\u4e0d\u548c\u8c10\u6c27\u5316\u6a21\u5f0f(dissonant oxidation pattern)\u4ee5\u53caC19\u7acb\u4f53\u5316\u5b66\u7b49\u7279\u70b9\u3002 \u57fa\u4e8e\u5176\u7279\u6b8a\u7684\u9aa8\u67b6\uff0c\u4f5c\u8005\u5bf9(\u2212)-Hunterine A(1)\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u9006\u5408\u6210\u5206\u6790(Scheme 1A)\uff0c\u5373\u5bf9\u79f0\u4e8c\u916e6\u7ecf\u53bb\u5bf9\u79f0\u5316\u548c\u91cd\u6392\u6765\u6784\u5efa\u780c\u57575\uff0c4\u548c5\u901a\u8fc7\u6c47\u805a\u5f0f\u548c\u975e\u5bf9\u6620\u9009\u62e9\u60271,2-\u52a0\u6210\u53cd\u5e94\u5236\u5907\u780c\u57573\u3002\u968f\u540e\uff0c3\u7ecfaza-Cope\/Mannich \u91cd\u6392\u53cd\u5e94\u83b7\u5f97\u4e2d\u95f4\u4f532\u3002\u6700\u540e\uff0c2\u7ecf\u8fc7\u540e\u671f\u5b98\u80fd\u56e2\u4fee\u9970\u5b8c\u6210\u5929\u7136\u4ea7\u7269(\u2212)-Hunterine A(1)\u7684\u5168\u5408\u6210\u3002\u57fa\u4e8e1\u4e2d\u4e0d\u542b\u5432\u54da\uff0cC7\u5168\u78b3\u56db\u5143\u4e2d\u5fc3\u4e0d\u53ef\u4f7f\u7528\u5176\u4ed6\u76f8\u5173MIAs\u7684\u5408\u6210\u7b56\u7565\uff0c\u540e\u8005\u901a\u5e38\u91c7\u7528Fischer\u5432\u54da\u5408\u6210\u548c\u4eb2\u6838\u5432\u54da\u70f7\u57fa\u5316(\u65b9\u68481B)\u7b49\u7b56\u7565\u3002 […]","protected":false},"author":26,"featured_media":49213,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"jetpack_post_was_ever_published":false,"_jetpack_newsletter_access":"","_jetpack_dont_email_post_to_subs":false,"_jetpack_newsletter_tier_id":0,"_jetpack_memberships_contains_paywalled_content":false,"_jetpack_memberships_contains_paid_content":false,"footnotes":"","jetpack_publicize_message":"","jetpack_publicize_feature_enabled":true,"jetpack_social_post_already_shared":true,"jetpack_social_options":{"image_generator_settings":{"template":"highway","enabled":false},"version":2}},"categories":[1271],"tags":[],"jetpack_publicize_connections":[],"jetpack_featured_media_url":"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/03\/image002-1.gif","jetpack_shortlink":"https:\/\/wp.me\/p96op1-cNK","jetpack_sharing_enabled":true,"_links":{"self":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/49212"}],"collection":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/users\/26"}],"replies":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/comments?post=49212"}],"version-history":[{"count":2,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/49212\/revisions"}],"predecessor-version":[{"id":49222,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/49212\/revisions\/49222"}],"wp:featuredmedia":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media\/49213"}],"wp:attachment":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media?parent=49212"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/categories?post=49212"},{"taxonomy":"post_tag","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/tags?post=49212"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}