{"id":48561,"date":"2024-01-24T09:25:15","date_gmt":"2024-01-24T01:25:15","guid":{"rendered":"\/\/www.gsbet888.com\/?p=48561"},"modified":"2024-01-24T09:26:35","modified_gmt":"2024-01-24T01:26:35","slug":"jacs%ef%bc%9a%e5%a4%a9%e7%84%b6%e4%ba%a7%e7%89%a9%e2%88%92-daphenylline%e7%9a%84%e5%85%a8%e5%90%88%e6%88%90","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/reactions\/2024\/01\/jacs%ef%bc%9a%e5%a4%a9%e7%84%b6%e4%ba%a7%e7%89%a9%e2%88%92-daphenylline%e7%9a%84%e5%85%a8%e5%90%88%e6%88%90.html","title":{"rendered":"JACS\uff1a\u5929\u7136\u4ea7\u7269(\u2212)-Daphenylline\u7684\u5168\u5408\u6210"},"content":{"rendered":"<p><strong>\u4f5c\u8005\uff1a\u77f3\u6cb9\u919a<\/strong><\/p>\n<h4>\u5bfc\u8bfb\uff1a<\/h4>\n<p>\u8fd1\u65e5\uff0c\u4e2d\u79d1\u9662\u6606\u660e\u690d\u7269\u7814\u7a76\u6240\u7684\u6768\u7389\u8363\u7814\u7a76\u5458\u56e2\u961f\u5728<em>J. Am. Chem. Soc.<\/em>\u4e0a\uff0c\u4ee5 \u201cEnantioselective Total Synthesis of (\u2212)-Daphenylline\u201d \u4e3a\u9898\uff0c\u62a5\u9053\u4e86\u516d\u73afDaphniphyllum \u751f\u7269\u78b1(\u2212)-Daphenylline\u7684\u7b80\u6d01\u5168\u5408\u6210\u3002\u5176\u4e2d\u5173\u952e\u6b65\u9aa4\u6d89\u53ca1\uff09Carreira\u94f1\/\u80fa\u53cc\u5143\u50ac\u5316\u70ef\u4e19\u57fa\u5316(Carreira\u2019s Ir\/amine dual-catalyzed allylation.)\u6784\u5efa\u4e24\u4e2a\u624b\u6027\u7acb\u4f53\u4e2d\u5fc3\uff1b2\uff09Wickens\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u70ef\u70c3\u7684\u6c22\u7fa7\u57fa\u5316(Wickens\u2019 photoredox-catalyzed hydrocarboxylation of olefin)\u548cCuBr<sub>2<\/sub>\u50ac\u5316\u916e\u7684\u03b1-\u80fa\u5316\u7b496\u6b65\u5feb\u901f\u5236\u5907\u6865\u5934\u70ef\u4e19\u57fa\u80fa\u4e2d\u95f4\u4f53\uff1b3\uff09Pd\u50ac\u5316\u7684\u8fd8\u539fHeck\u53cd\u5e94(Pd-catalyzed reductive Heck reaction)\u6216Krische Rh\u50ac\u5316\u8fd8\u539f1,6-\u7094\u73af\u5316(Krische\u2019s Rh-catalyzed reductive 1,6-enyne cyclization)\u6784\u5efa\u56db\u73af\u9aa8\u67b6\u3002\u6b64\u5916\uff0c\u5728\u6b64\u5408\u6210\u4e2dWickens\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u7684\u6c22\u7fa7\u57fa\u5316\u4f7f\u7528\u4e24\u6b21\uff0cFriedel-Crafts\u9170\u5316\u4f7f\u7528\u4e09\u6b21\u3002<\/p>\n<blockquote><p>\u201cEnantioselective Total Synthesis of (\u2212)-Daphenylline<\/p>\n<p>Bing-Lu Wu, Jian-Neng Yao, Xiang-Xi Long, Zong-Qin Tan, Xiao Liang, Li Feng, Kun Wei, and Yu-Rong Yang*<\/p>\n<p><em>J. Am. Chem. Soc.<\/em>, <strong>2024. <\/strong><em>ASAP<\/em>. doi: <a href=\"https:\/\/doi.org\/10.1021\/jacs.3c00753\">10.1021\/jacs.3c12741\u201d<\/a><\/p><\/blockquote>\n<h4>\u6b63\u6587<\/h4>\n<p><em>Daphniphyllum<\/em>\u751f\u7269\u78b1\u662f\u7531Yagi\u4e8e1910\u5e74\u9996\u6b21\u4ece\u843d\u53f6\u6811Yuzuriha\u4e2d\u9996\u6b21\u5206\u79bb\u83b7\u5f97\u7684\u4e00\u79cd\u5177\u6709\u7684\u4e00\u7c7b\u591a\u73af\u5929\u7136\u4ea7\u7269\u3002\u4e00\u767e\u591a\u5e74\uff0c\u79d1\u5b66\u5bb6\u5df2\u7ecf\u5206\u79bb\u8868\u5f81\u4e86300\u591a\u4e2a\u8be5\u5bb6\u65cf\u7684\u6210\u5458\u3002<em>Daphniphyllum<\/em>\u751f\u7269\u78b1\u56e0\u5176\u590d\u6742\u591a\u6837\u7684\u5316\u5b66\u7ed3\u6784\u4ee5\u53ca\u5305\u62ec\u6297\u764c\u3001\u6297\u6c27\u5316\u3001\u6297\u827e\u6ecb\u75c5\u3001\u4fc3\u8fdb\u795e\u7ecf\u751f\u957f\u56e0\u5b50\u7b49\u5e7f\u6cdb\u7684\u751f\u7269\u6d3b\u6027\u5f15\u8d77\u4e86\u4f17\u591a\u79d1\u5b66\u5bb6\u6781\u5927\u7684\u5173\u6ce8<sup>[1]<\/sup>\u300220\u4e16\u7eaa80\u5e74\u4ee3\uff0cHeathcock\u7b49\u4eba\u9996\u6b21\u5b8c\u6210<em>Daphniphyllum<\/em>\u751f\u7269\u78b1methyl homosecodaphniphyllate\u7684\u5168\u5408\u6210<sup>[2]<\/sup>\u30022011\u5e74\uff0cCarreira<sup>[3]<\/sup>\u548cWeiss\u5b8c\u6210\u4e86(+)-daphmanidin E\u7684\u5168\u5408\u6210\u3002\u6b64\u540e\uff0c\u8bb8\u591a\u79d1\u5b66\u5bb6\u5b8c\u6210\u591a\u4e2a\u5177\u6709\u6311\u6218\u6027\u7ed3\u6784\u7684<em>Daphniphyllum<\/em>\u751f\u7269\u78b1\u5168\u5408\u6210<sup>[4]<\/sup>\uff0c\u7279\u522b\u662f\u674e\u6602\uff0c Smith\uff0cFukuyama\uff0cHanessian\uff0cDixon\uff0c\u7fdf\u5b8f\u658c\uff0c\u90b1\u53d1\u6d0b\uff0c\u5f90\u6676\uff0c\u9ad8\u6813\u864e\uff0cSarpong\uff0c\u674e\u8d85\uff0c\u9646\u6d77\u534e\u548c\u674e\u95ef\u521b\u5206\u522b\u5b8c\u6210\u4e86Daphniphyllum\u751f\u7269\u78b1\u7684\u4e00\u4e2a\u6216\u591a\u4e2a\u5bb6\u65cf\u6210\u5458\u7684\u5168\u5408\u6210(Figure 1)\u3002\u4e0a\u8ff0\u4f17\u591a\u79d1\u5b66\u5bb6\u5728\u5168\u5408\u6210\u4e2d\u7684\u5de5\u4f5c\u4e0d\u4ec5\u4e30\u5bcc\u4e86\u7528\u4e8e\u590d\u6742\u9776\u70b9\u7684\u65b0\u7b56\u7565\u548c\u65b0\u65b9\u6cd5\uff0c\u800c\u4e14\u4fc3\u8fdb\u4e86\u5bf9\u751f\u7269\u5408\u6210\u4e0e\u5316\u5b66\u7ed3\u6784\u4e4b\u95f4\u5185\u5728\u76f8\u5173\u6027\u7684\u7406\u89e3\uff0c\u8fdb\u800c\u8865\u5145\u4e86Heathcock\u7684\u89d2\u9ca8\u70ef\u731c\u60f3<sup>[5]<\/sup>\u3002<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-48564 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/01\/image004-1.gif\" alt=\"\" width=\"448\" height=\"580\" \/><\/p>\n<p>\u5929\u7136\u4ea7\u7269(\u2212)-Daphenylline\u662f<em>Daphniphyllum<\/em>\u751f\u7269\u78b1\u5bb6\u65cf\u4e2d\u5177\u6709\u7ed3\u6784\u72ec\u7279\u7684\u6210\u5458\u4e4b\u4e00\uff0c\u5176\u662f\u7531\u4e2d\u56fd\u79d1\u5b66\u9662\u90dd\u5c0f\u6c5f\u9662\u58eb\u53ca\u5176\u540c\u4e8b\u4e8e2009\u5e74\u9996\u6b21\u5206\u79bb\u83b7\u5f97<sup>[6]<\/sup>\u3002Daphenylline\u56e0\u5176\u5b83\u5177\u6709\u72ec\u72791,2,3,4-\u56db\u53d6\u4ee3\u82ef\u73af\u7ed3\u6784\uff0c\u8fdb\u800c\u5728calyciphylline A-\u578b\u751f\u7269\u78b1\u4e2d\u8131\u9896\u800c\u51fa\uff0c\u6210\u4e3a\u5168\u5408\u6210\u7684\u7406\u60f3\u76ee\u6807(Figure 2)\uff0c\u59821\uff09\u674e\u6602\u7814\u7a76\u5458\u4ee56\u03c0-\u7535\u73af\u5316\u4e3a\u5173\u952e\u6b65\u9aa4\u9996\u6b21\u5b8c\u6210\u4e86(-)Daphenylline\u7684\u5168\u5408\u6210 (2013)<sup>[7]<\/sup>\uff1b2\uff09 Fukuyama\u6559\u6388\u4ee51,3-\u5076\u6781\u73af\u52a0\u6210\u7684\u5173\u952e\u6b65\u9aa4\u5b8c\u6210\u4e86\u8be5\u5206\u5b50\u7684\u5168\u5408\u6210(2016)<sup> [8]<\/sup>\uff1b3\uff09 \u674e\u6602\u7814\u7a76\u5458<sup>[9]<\/sup>\u548c\u7fdf\u5b8f\u658c<sup>[10]<\/sup>\u6559\u6388\u5206\u8d1d\u91c7\u7528\u4eff\u751f\u91cd\u6392\u4e3a\u4e3b\u8981\u7b56\u7565\u7b56\u7565\u5b8c\u6210\u8be5\u5206\u5b50\u7684\u6784\u5efa(2018)\uff1b4\uff09\u90b1\u53d1\u6d0b\u4ee5Diels-Alder\u53cd\u5e94\u4e3a\u5173\u952e\u53cd\u5e94\u6784\u5efa\u8be5\u5206\u5b50\u7684\u9aa8\u67b6<sup>[11, 12]<\/sup> (2019)\uff082021\uff09\uff1b5) \u9646\u6d77\u534e\u6559\u6388\u4ee5\u6c27\u5316\u8131\u82b3\u6784\u5316\u7684\u7b56\u7565\u5b9e\u73b0\u6b64\u5206\u5b50\u7684\u5408\u6210<sup>[13]<\/sup>\u3002\u8fd1\u65e5\uff0c\u4e2d\u79d1\u9662\u6606\u660e\u690d\u7269\u7814\u7a76\u6240\u7684\u6768\u7389\u8363\u7814\u7a76\u5458\u56e2\u961f\u4ece\u7b80\u5355\u6613\u5f97\u539f\u6599\u51fa\u53d1\uff0c\u4ec5\u970014\u6b65\u53cd\u5e94\u6210\u529f\u5b9e\u73b0\u516d\u73afDaphniphyllum \u751f\u7269\u78b1(\u2212)-daphenylline\u7684\u7b80\u6d01\u5168\u5408\u6210\u3002\u5e76\u53d1\u8868\u4e8e<em>J. Am. Chem. Soc.<\/em>\u4e0a\u3002<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-48565 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/01\/image006-1.gif\" alt=\"\" width=\"554\" height=\"262\" \/><\/p>\n<p>\u5929\u7136\u4ea7\u7269(\u2212)-Daphenylline\u662f\u552f\u4e00\u4e00\u4e2a\u5177\u6709\u82ef\u73af6\/6\/6\/5\/7\/5\u516d\u73af\u7a20\u5408\u7684\u864e\u76ae\u6960\u751f\u7269\u78b1\uff0c\u5206\u5b50\u4e2d\u5177\u6709\u6c2e\u6742\u4e8c\u73af[3.3.1]\u58ec\u70f7\u7ed3\u6784\u5355\u5143\uff0c6\u4e2a\u624b\u6027\u4e2d\u5fc3\uff0c\u5176\u4e2d\u4e00\u4e2a\u662f\u5168\u78b3\u7684\u5b63\u78b3\u4e2d\u5fc3(Figure 2)\u3002\u57fa\u4e8e\u4e0a\u8ff0\u7ed3\u6784\uff0c\u4f5c\u8005\u5bf9(\u2212)-Daphenylline (<strong>1<\/strong>)\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u9006\u5408\u6210\u5206\u6790(Scheme 1)\u3002\u5373\u4ee5\u5e02\u552e\u7684\u70ef\u4e19\u9187\u548c\u4e19\u919b\u7ecfCarreira\u2019s \u94f1\/\u80fa\u53cc\u5143\u50ac\u5316\u70ef\u4e19\u57fa\u5316<sup>[14]<\/sup>\u6784\u5efa\u4e24\u4e2a\u53d4\u78b3\u7acb\u4f53\u4e2d\u5fc3\u6784\u5efa\u780c\u5757(<strong>12<\/strong>)\uff0c(<strong>12<\/strong>)\u7ecf\u8fd8\u539f\u80fa\u5316\u6784\u5efa(<strong>11<\/strong>)\uff0c(<strong>11<\/strong>)\u901a\u8fc7\u5355-\u78b3\u540c\u7cfb\u5316\u548cFriedel\u2013Crafts\u9170\u5316\u53cd\u5e94\u5408\u6210(<strong>10<\/strong>)\uff0c(<strong>10<\/strong>)\u7ecf\u916e\u03b1-\u80fa\u5316\u5408\u6210\u6865\u5934\u80fa\u4e2d\u95f4\u4f53(<strong>8<\/strong>)\u3002\u53e6\u5916\uff0c(<strong>12<\/strong>)\u7ecf\u8fd8\u539f\u548c\u6c2f\u4ee3\u6784\u5efa(<strong>9<\/strong>)\uff0c(<strong>9<\/strong>)\u901a\u8fc7\u5355-\u78b3\u540c\u7cfb\u5316\u548cFriedel\u2013Crafts\u9170\u5316\u53cd\u5e94\u5408\u6210(<strong>7<\/strong>)\u3002\u968f\u540e\uff0c(<strong>7<\/strong>)\u901a\u8fc7\u53e0\u6c2e\u548c\u70ef\u70c31,3-\u5076\u6781\u73af\u52a0\u6210<sup>[15]<\/sup>\u6216(<strong>8<\/strong>)\u7ecfWittig\u53cd\u5e94\u751f\u6210\u6865\u5934\u70ef\u4e19\u57fa\u80fa\u4e2d\u95f4\u4f53(<strong>6<\/strong>)\u3002(<strong>6<\/strong>)\u7ecf\u8fc7\u5076\u8054\u5408\u6210\u4e2d\u95f4\u4f53(<strong>5<\/strong>)\uff0c(<strong>5<\/strong>)\u901a\u8fc7 Pd\u50ac\u5316\u7684\u8fd8\u539fHeck\u53cd\u5e94<sup>[16]<\/sup>\u6216Krische\u2019s Rh\u50ac\u5316\u8fd8\u539f1,6-\u7094\u73af\u5316<sup>[17]<\/sup>\u6784\u5efa\u56db\u73af\u9aa8\u67b6(<strong>4<\/strong>)\uff0c(<strong>4<\/strong>)\u901a\u8fc7\u4e24\u6b21Friedel\u2013Crafts\u53cd\u5e94\u5408\u6210\u5173\u952e\u780c\u5757(<strong>2<\/strong>)\u3002\u6700\u540e\uff0c(<strong>2<\/strong>)\u7ecf\u8fd8\u539f\u53cd\u5e94\u5b8c\u6210\u5929\u7136\u4ea7\u7269(\u2212)-Daphenylline\u7684\u5168\u5408\u6210\u3002<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-48566 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/01\/image008-1.gif\" alt=\"\" width=\"554\" height=\"495\" \/><\/p>\n<p>\u9996\u5148\uff0c\u4f5c\u8005\u901a\u8fc7\u4e24\u79cd\u65b9\u6cd5\u5bf9\u4e2d\u95f4\u4f53(<strong>6<\/strong>)\u8fdb\u884c\u4e86\u76f8\u5173\u5408\u6210\u5206\u6790\uff0c\u89c1Scheme 2 \u6240\u793a\u3002<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-48567 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/01\/image010-1.gif\" alt=\"\" width=\"554\" height=\"489\" \/><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-48572 \" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/01\/7678de6506c79b3d4d6fdff512506d15.png\" alt=\"\" width=\"598\" height=\"440\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/01\/7678de6506c79b3d4d6fdff512506d15.png 696w, https:\/\/assets.www.gsbet888.com\/uploads\/2024\/01\/7678de6506c79b3d4d6fdff512506d15-300x221.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2024\/01\/7678de6506c79b3d4d6fdff512506d15-680x500.png 680w\" sizes=\"(max-width: 598px) 100vw, 598px\" \/><\/p>\n<p>\u6700\u540e\uff0c\u4f5c\u8005\u5b8c\u6210\u4e86\u5929\u7136\u4ea7\u7269(\u2212)-Daphenylline\u7684\u5168\u5408\u6210\uff0c\u89c1Scheme 3 \u6240\u793a\u3002<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-48569 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/01\/image014-1.gif\" alt=\"\" width=\"553\" height=\"437\" \/> \u00a0<img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-48571 \" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/01\/c7aa3225a800bc68019274a44751b098.png\" alt=\"\" width=\"572\" height=\"227\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/01\/c7aa3225a800bc68019274a44751b098.png 780w, https:\/\/assets.www.gsbet888.com\/uploads\/2024\/01\/c7aa3225a800bc68019274a44751b098-300x119.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2024\/01\/c7aa3225a800bc68019274a44751b098-680x270.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2024\/01\/c7aa3225a800bc68019274a44751b098-768x305.png 768w\" sizes=\"(max-width: 572px) 100vw, 572px\" \/><\/p>\n<p>\u603b\u7ed3\uff0c\u6768\u7389\u8363\u7814\u7a76\u5458\u56e2\u961f\u4ece\u7b80\u5355\u6613\u5f97\u539f\u6599\u51fa\u53d1\uff0c\u4ec5\u970014\u6b65\u53cd\u5e94\u6210\u529f\u5b9e\u73b0\u516d\u73afDaphniphyllum \u751f\u7269\u78b1(\u2212)-daphenylline\u7684\u7b80\u6d01\u5168\u5408\u6210\u3002\u5176\u4e2d\u5173\u952e\u6b65\u9aa4\u6d89\u53ca1\uff09Carreira\u94f1\/\u80fa\u53cc\u5143\u50ac\u5316\u70ef\u4e19\u57fa\u5316(Carreira\u2019s Ir\/amine dual-catalyzed allylation.)\u6784\u5efa\u4e24\u4e2a\u624b\u6027\u7acb\u4f53\u4e2d\u5fc3\uff1b2\uff09Wickens\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u70ef\u70c3\u7684\u6c22\u7fa7\u57fa\u5316(Wickens\u2019 photoredox-catalyzed hydrocarboxylation of olefin)\u548cCuBr<sub>2<\/sub>\u50ac\u5316\u916e\u7684\u03b1-\u80fa\u5316\u7b496\u6b65\u5feb\u901f\u5236\u5907\u6865\u5934\u70ef\u4e19\u57fa\u80fa\u4e2d\u95f4\u4f53\uff1b3\uff09Pd\u50ac\u5316\u7684\u8fd8\u539fHeck\u53cd\u5e94\u6216Krische Rh\u50ac\u5316\u8fd8\u539f1,6-\u7094\u73af\u5316\u6784\u5efa\u56db\u73af\u9aa8\u67b6\u3002<\/p>\n<h4>\u53c2\u8003\u6587\u732e:<\/h4>\n<ul>\n<li>[1] J. i. 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Huisgen, <strong>1963<\/strong>, <em>2<\/em>, 565. doi:<a href=\"https:\/\/doi.org\/10.1002\/anie.196305651\">10.1002\/anie.196305651<\/a>.<\/li>\n<li>[16] S. Cacchi, A. Arcadi, <em>J. Org. Chem. <\/em><strong>1983<\/strong>, <em>48<\/em>, 4236. doi:<a href=\"https:\/\/pubs.acs.org\/doi\/abs\/10.1021\/jo00171a016\">10.1021\/jo00171a016.<\/a><\/li>\n<li>[17] H.-Y. Jang, F. W. Hughes, H. Gong, J. Zhang, J. S. Brodbelt, M. J. Krische, <em>J. Am. Chem. Soc. <\/em><strong>2005<\/strong>, <em>127<\/em>, 6174. doi:<a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/ja042645v\">10.1021\/ja042645v.<\/a><\/li>\n<li>[18] S. N. Alektiar, J. Han, Y. Dang, C. Z. Rubel, Z. K. Wickens, <em>J. Am. Chem. Soc. <\/em><strong>2023<\/strong>, <em>145<\/em>, 10991. doi:<a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/jacs.3c03671\">10.1021\/jacs.3c03671.<\/a><\/li>\n<\/ul>\n<p>\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<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"\u4f5c\u8005\uff1a\u77f3\u6cb9\u919a \u5bfc\u8bfb\uff1a \u8fd1\u65e5\uff0c\u4e2d\u79d1\u9662\u6606\u660e\u690d\u7269\u7814\u7a76\u6240\u7684\u6768\u7389\u8363\u7814\u7a76\u5458\u56e2\u961f\u5728J. Am. Chem. Soc.\u4e0a\uff0c\u4ee5 \u201cEnantioselective Total Synthesis of (\u2212)-Daphenylline\u201d \u4e3a\u9898\uff0c\u62a5\u9053\u4e86\u516d\u73afDaphniphyllum \u751f\u7269\u78b1(\u2212)-Daphenylline\u7684\u7b80\u6d01\u5168\u5408\u6210\u3002\u5176\u4e2d\u5173\u952e\u6b65\u9aa4\u6d89\u53ca1\uff09Carreira\u94f1\/\u80fa\u53cc\u5143\u50ac\u5316\u70ef\u4e19\u57fa\u5316(Carreira\u2019s Ir\/amine dual-catalyzed allylation.)\u6784\u5efa\u4e24\u4e2a\u624b\u6027\u7acb\u4f53\u4e2d\u5fc3\uff1b2\uff09Wickens\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u70ef\u70c3\u7684\u6c22\u7fa7\u57fa\u5316(Wickens\u2019 photoredox-catalyzed hydrocarboxylation of olefin)\u548cCuBr2\u50ac\u5316\u916e\u7684\u03b1-\u80fa\u5316\u7b496\u6b65\u5feb\u901f\u5236\u5907\u6865\u5934\u70ef\u4e19\u57fa\u80fa\u4e2d\u95f4\u4f53\uff1b3\uff09Pd\u50ac\u5316\u7684\u8fd8\u539fHeck\u53cd\u5e94(Pd-catalyzed reductive Heck reaction)\u6216Krische Rh\u50ac\u5316\u8fd8\u539f1,6-\u7094\u73af\u5316(Krische\u2019s Rh-catalyzed reductive 1,6-enyne cyclization)\u6784\u5efa\u56db\u73af\u9aa8\u67b6\u3002\u6b64\u5916\uff0c\u5728\u6b64\u5408\u6210\u4e2dWickens\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u7684\u6c22\u7fa7\u57fa\u5316\u4f7f\u7528\u4e24\u6b21\uff0cFriedel-Crafts\u9170\u5316\u4f7f\u7528\u4e09\u6b21\u3002 \u201cEnantioselective Total Synthesis of (\u2212)-Daphenylline Bing-Lu Wu, Jian-Neng Yao, Xiang-Xi Long, Zong-Qin Tan, Xiao Liang, Li Feng, Kun Wei, and Yu-Rong Yang* J. Am. Chem. Soc., 2024. ASAP. doi: 10.1021\/jacs.3c12741\u201d \u6b63\u6587 Daphniphyllum\u751f\u7269\u78b1\u662f\u7531Yagi\u4e8e1910\u5e74\u9996\u6b21\u4ece\u843d\u53f6\u6811Yuzuriha\u4e2d\u9996\u6b21\u5206\u79bb\u83b7\u5f97\u7684\u4e00\u79cd\u5177\u6709\u7684\u4e00\u7c7b\u591a\u73af\u5929\u7136\u4ea7\u7269\u3002\u4e00\u767e\u591a\u5e74\uff0c\u79d1\u5b66\u5bb6\u5df2\u7ecf\u5206\u79bb\u8868\u5f81\u4e86300\u591a\u4e2a\u8be5\u5bb6\u65cf\u7684\u6210\u5458\u3002Daphniphyllum\u751f\u7269\u78b1\u56e0\u5176\u590d\u6742\u591a\u6837\u7684\u5316\u5b66\u7ed3\u6784\u4ee5\u53ca\u5305\u62ec\u6297\u764c\u3001\u6297\u6c27\u5316\u3001\u6297\u827e\u6ecb\u75c5\u3001\u4fc3\u8fdb\u795e\u7ecf\u751f\u957f\u56e0\u5b50\u7b49\u5e7f\u6cdb\u7684\u751f\u7269\u6d3b\u6027\u5f15\u8d77\u4e86\u4f17\u591a\u79d1\u5b66\u5bb6\u6781\u5927\u7684\u5173\u6ce8[1]\u300220\u4e16\u7eaa80\u5e74\u4ee3\uff0cHeathcock\u7b49\u4eba\u9996\u6b21\u5b8c\u6210Daphniphyllum\u751f\u7269\u78b1methyl homosecodaphniphyllate\u7684\u5168\u5408\u6210[2]\u30022011\u5e74\uff0cCarreira[3]\u548cWeiss\u5b8c\u6210\u4e86(+)-daphmanidin E\u7684\u5168\u5408\u6210\u3002\u6b64\u540e\uff0c\u8bb8\u591a\u79d1\u5b66\u5bb6\u5b8c\u6210\u591a\u4e2a\u5177\u6709\u6311\u6218\u6027\u7ed3\u6784\u7684Daphniphyllum\u751f\u7269\u78b1\u5168\u5408\u6210[4]\uff0c\u7279\u522b\u662f\u674e\u6602\uff0c Smith\uff0cFukuyama\uff0cHanessian\uff0cDixon\uff0c\u7fdf\u5b8f\u658c\uff0c\u90b1\u53d1\u6d0b\uff0c\u5f90\u6676\uff0c\u9ad8\u6813\u864e\uff0cSarpong\uff0c\u674e\u8d85\uff0c\u9646\u6d77\u534e\u548c\u674e\u95ef\u521b\u5206\u522b\u5b8c\u6210\u4e86Daphniphyllum\u751f\u7269\u78b1\u7684\u4e00\u4e2a\u6216\u591a\u4e2a\u5bb6\u65cf\u6210\u5458\u7684\u5168\u5408\u6210(Figure 1)\u3002\u4e0a\u8ff0\u4f17\u591a\u79d1\u5b66\u5bb6\u5728\u5168\u5408\u6210\u4e2d\u7684\u5de5\u4f5c\u4e0d\u4ec5\u4e30\u5bcc\u4e86\u7528\u4e8e\u590d\u6742\u9776\u70b9\u7684\u65b0\u7b56\u7565\u548c\u65b0\u65b9\u6cd5\uff0c\u800c\u4e14\u4fc3\u8fdb\u4e86\u5bf9\u751f\u7269\u5408\u6210\u4e0e\u5316\u5b66\u7ed3\u6784\u4e4b\u95f4\u5185\u5728\u76f8\u5173\u6027\u7684\u7406\u89e3\uff0c\u8fdb\u800c\u8865\u5145\u4e86Heathcock\u7684\u89d2\u9ca8\u70ef\u731c\u60f3[5]\u3002 \u5929\u7136\u4ea7\u7269(\u2212)-Daphenylline\u662fDaphniphyllum\u751f\u7269\u78b1\u5bb6\u65cf\u4e2d\u5177\u6709\u7ed3\u6784\u72ec\u7279\u7684\u6210\u5458\u4e4b\u4e00\uff0c\u5176\u662f\u7531\u4e2d\u56fd\u79d1\u5b66\u9662\u90dd\u5c0f\u6c5f\u9662\u58eb\u53ca\u5176\u540c\u4e8b\u4e8e2009\u5e74\u9996\u6b21\u5206\u79bb\u83b7\u5f97[6]\u3002Daphenylline\u56e0\u5176\u5b83\u5177\u6709\u72ec\u72791,2,3,4-\u56db\u53d6\u4ee3\u82ef\u73af\u7ed3\u6784\uff0c\u8fdb\u800c\u5728calyciphylline A-\u578b\u751f\u7269\u78b1\u4e2d\u8131\u9896\u800c\u51fa\uff0c\u6210\u4e3a\u5168\u5408\u6210\u7684\u7406\u60f3\u76ee\u6807(Figure 2)\uff0c\u59821\uff09\u674e\u6602\u7814\u7a76\u5458\u4ee56\u03c0-\u7535\u73af\u5316\u4e3a\u5173\u952e\u6b65\u9aa4\u9996\u6b21\u5b8c\u6210\u4e86(-)Daphenylline\u7684\u5168\u5408\u6210 (2013)[7]\uff1b2\uff09 Fukuyama\u6559\u6388\u4ee51,3-\u5076\u6781\u73af\u52a0\u6210\u7684\u5173\u952e\u6b65\u9aa4\u5b8c\u6210\u4e86\u8be5\u5206\u5b50\u7684\u5168\u5408\u6210(2016) [8]\uff1b3\uff09 \u674e\u6602\u7814\u7a76\u5458[9]\u548c\u7fdf\u5b8f\u658c[10]\u6559\u6388\u5206\u8d1d\u91c7\u7528\u4eff\u751f\u91cd\u6392\u4e3a\u4e3b\u8981\u7b56\u7565\u7b56\u7565\u5b8c\u6210\u8be5\u5206\u5b50\u7684\u6784\u5efa(2018)\uff1b4\uff09\u90b1\u53d1\u6d0b\u4ee5Diels-Alder\u53cd\u5e94\u4e3a\u5173\u952e\u53cd\u5e94\u6784\u5efa\u8be5\u5206\u5b50\u7684\u9aa8\u67b6[11, 12] (2019)\uff082021\uff09\uff1b5) \u9646\u6d77\u534e\u6559\u6388\u4ee5\u6c27\u5316\u8131\u82b3\u6784\u5316\u7684\u7b56\u7565\u5b9e\u73b0\u6b64\u5206\u5b50\u7684\u5408\u6210[13]\u3002\u8fd1\u65e5\uff0c\u4e2d\u79d1\u9662\u6606\u660e\u690d\u7269\u7814\u7a76\u6240\u7684\u6768\u7389\u8363\u7814\u7a76\u5458\u56e2\u961f\u4ece\u7b80\u5355\u6613\u5f97\u539f\u6599\u51fa\u53d1\uff0c\u4ec5\u970014\u6b65\u53cd\u5e94\u6210\u529f\u5b9e\u73b0\u516d\u73afDaphniphyllum \u751f\u7269\u78b1(\u2212)-daphenylline\u7684\u7b80\u6d01\u5168\u5408\u6210\u3002\u5e76\u53d1\u8868\u4e8eJ. Am. Chem. Soc.\u4e0a\u3002 \u5929\u7136\u4ea7\u7269(\u2212)-Daphenylline\u662f\u552f\u4e00\u4e00\u4e2a\u5177\u6709\u82ef\u73af6\/6\/6\/5\/7\/5\u516d\u73af\u7a20\u5408\u7684\u864e\u76ae\u6960\u751f\u7269\u78b1\uff0c\u5206\u5b50\u4e2d\u5177\u6709\u6c2e\u6742\u4e8c\u73af[3.3.1]\u58ec\u70f7\u7ed3\u6784\u5355\u5143\uff0c6\u4e2a\u624b\u6027\u4e2d\u5fc3\uff0c\u5176\u4e2d\u4e00\u4e2a\u662f\u5168\u78b3\u7684\u5b63\u78b3\u4e2d\u5fc3(Figure 2)\u3002\u57fa\u4e8e\u4e0a\u8ff0\u7ed3\u6784\uff0c\u4f5c\u8005\u5bf9(\u2212)-Daphenylline (1)\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u9006\u5408\u6210\u5206\u6790(Scheme 1)\u3002\u5373\u4ee5\u5e02\u552e\u7684\u70ef\u4e19\u9187\u548c\u4e19\u919b\u7ecfCarreira\u2019s \u94f1\/\u80fa\u53cc\u5143\u50ac\u5316\u70ef\u4e19\u57fa\u5316[14]\u6784\u5efa\u4e24\u4e2a\u53d4\u78b3\u7acb\u4f53\u4e2d\u5fc3\u6784\u5efa\u780c\u5757(12)\uff0c(12)\u7ecf\u8fd8\u539f\u80fa\u5316\u6784\u5efa(11)\uff0c(11)\u901a\u8fc7\u5355-\u78b3\u540c\u7cfb\u5316\u548cFriedel\u2013Crafts\u9170\u5316\u53cd\u5e94\u5408\u6210(10)\uff0c(10)\u7ecf\u916e\u03b1-\u80fa\u5316\u5408\u6210\u6865\u5934\u80fa\u4e2d\u95f4\u4f53(8)\u3002\u53e6\u5916\uff0c(12)\u7ecf\u8fd8\u539f\u548c\u6c2f\u4ee3\u6784\u5efa(9)\uff0c(9)\u901a\u8fc7\u5355-\u78b3\u540c\u7cfb\u5316\u548cFriedel\u2013Crafts\u9170\u5316\u53cd\u5e94\u5408\u6210(7)\u3002\u968f\u540e\uff0c(7)\u901a\u8fc7\u53e0\u6c2e\u548c\u70ef\u70c31,3-\u5076\u6781\u73af\u52a0\u6210[15]\u6216(8)\u7ecfWittig\u53cd\u5e94\u751f\u6210\u6865\u5934\u70ef\u4e19\u57fa\u80fa\u4e2d\u95f4\u4f53(6)\u3002(6)\u7ecf\u8fc7\u5076\u8054\u5408\u6210\u4e2d\u95f4\u4f53(5)\uff0c(5)\u901a\u8fc7 Pd\u50ac\u5316\u7684\u8fd8\u539fHeck\u53cd\u5e94[16]\u6216Krische\u2019s Rh\u50ac\u5316\u8fd8\u539f1,6-\u7094\u73af\u5316[17]\u6784\u5efa\u56db\u73af\u9aa8\u67b6(4)\uff0c(4)\u901a\u8fc7\u4e24\u6b21Friedel\u2013Crafts\u53cd\u5e94\u5408\u6210\u5173\u952e\u780c\u5757(2)\u3002\u6700\u540e\uff0c(2)\u7ecf\u8fd8\u539f\u53cd\u5e94\u5b8c\u6210\u5929\u7136\u4ea7\u7269(\u2212)-Daphenylline\u7684\u5168\u5408\u6210\u3002 \u9996\u5148\uff0c\u4f5c\u8005\u901a\u8fc7\u4e24\u79cd\u65b9\u6cd5\u5bf9\u4e2d\u95f4\u4f53(6)\u8fdb\u884c\u4e86\u76f8\u5173\u5408\u6210\u5206\u6790\uff0c\u89c1Scheme 2 \u6240\u793a\u3002 \u6700\u540e\uff0c\u4f5c\u8005\u5b8c\u6210\u4e86\u5929\u7136\u4ea7\u7269(\u2212)-Daphenylline\u7684\u5168\u5408\u6210\uff0c\u89c1Scheme 3 \u6240\u793a\u3002 \u00a0 \u603b\u7ed3\uff0c\u6768\u7389\u8363\u7814\u7a76\u5458\u56e2\u961f\u4ece\u7b80\u5355\u6613\u5f97\u539f\u6599\u51fa\u53d1\uff0c\u4ec5\u970014\u6b65\u53cd\u5e94\u6210\u529f\u5b9e\u73b0\u516d\u73afDaphniphyllum \u751f\u7269\u78b1(\u2212)-daphenylline\u7684\u7b80\u6d01\u5168\u5408\u6210\u3002\u5176\u4e2d\u5173\u952e\u6b65\u9aa4\u6d89\u53ca1\uff09Carreira\u94f1\/\u80fa\u53cc\u5143\u50ac\u5316\u70ef\u4e19\u57fa\u5316(Carreira\u2019s Ir\/amine dual-catalyzed allylation.)\u6784\u5efa\u4e24\u4e2a\u624b\u6027\u7acb\u4f53\u4e2d\u5fc3\uff1b2\uff09Wickens\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u70ef\u70c3\u7684\u6c22\u7fa7\u57fa\u5316(Wickens\u2019 photoredox-catalyzed hydrocarboxylation of olefin)\u548cCuBr2\u50ac\u5316\u916e\u7684\u03b1-\u80fa\u5316\u7b496\u6b65\u5feb\u901f\u5236\u5907\u6865\u5934\u70ef\u4e19\u57fa\u80fa\u4e2d\u95f4\u4f53\uff1b3\uff09Pd\u50ac\u5316\u7684\u8fd8\u539fHeck\u53cd\u5e94\u6216Krische Rh\u50ac\u5316\u8fd8\u539f1,6-\u7094\u73af\u5316\u6784\u5efa\u56db\u73af\u9aa8\u67b6\u3002 \u53c2\u8003\u6587\u732e: [1] J. i. Kobayashi, T. Kubota, Nat. 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