{"id":40109,"date":"2021-09-21T08:00:43","date_gmt":"2021-09-21T00:00:43","guid":{"rendered":"\/\/www.gsbet888.com\/?p=40109"},"modified":"2021-10-06T12:29:37","modified_gmt":"2021-10-06T04:29:37","slug":"%e9%92%af%e5%82%ac%e5%8c%96%e7%9a%84%e5%bc%a0%e5%8a%9b%e7%8e%af%e8%81%94%e7%83%af%e7%8e%af%e5%8c%96%e5%8f%8d%e5%ba%94%e6%96%b9%e6%b3%95%e5%ad%a6%e7%a0%94%e7%a9%b6","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2021\/09\/%e9%92%af%e5%82%ac%e5%8c%96%e7%9a%84%e5%bc%a0%e5%8a%9b%e7%8e%af%e8%81%94%e7%83%af%e7%8e%af%e5%8c%96%e5%8f%8d%e5%ba%94%e6%96%b9%e6%b3%95%e5%ad%a6%e7%a0%94%e7%a9%b6.html","title":{"rendered":"\u94af\u50ac\u5316\u7684\u5f20\u529b\u73af\u8054\u70ef\u73af\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u7814\u7a76"},"content":{"rendered":"<p><strong>\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749<\/strong><\/p>\n<h4>\u5bfc\u8bfb<\/h4>\n<p>\u8fd1\u65e5\uff0cCalifornia\u5927\u5b66\u7684N.\u00a0K. Garg\u6559\u6388\u8bfe\u9898\u7ec4\u5728<em>JACS<\/em>\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u5728\u94af\u50ac\u5316\u6761\u4ef6\u4e0b\uff0c\u901a\u8fc7\u539f\u4f4d\u5f62\u6210\u7684\u5f20\u529b\u73af\u8054\u70ef (strained cyclic allene)\u00a0\u53c2\u4e0e\u7684\u73af\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u3002\u8fd9\u4e00\u5168\u65b0\u7684\u73af\u5316\u7b56\u7565\u4e2d\u91c7\u7528\u82b3\u5364\u4e0e\u73af\u8054\u70ef\u524d\u4f53\uff0c\u4f5c\u4e3a\u53cd\u5e94\u53c2\u4e0e\u7269\uff0c\u8fdb\u800c\u6210\u529f\u5b8c\u6210\u4e00\u7cfb\u5217\u7a20\u6742\u73af\u5206\u5b50\u7684\u6784\u5efa\u3002\u540c\u65f6\uff0c\u4e0a\u8ff0\u7684\u73af\u5316\u8fc7\u7a0b\u4e2d\u6d89\u53ca\u4e24\u79cd\u4e0d\u540c\u7684\u65b0\u952e\u4ee5\u53ca\u4e00\u4e2asp<sup>3<\/sup>\u4e2d\u5fc3\u7684\u5f62\u6210\u3002\u6b64\u5916\uff0c\u8fd9\u4e00\u65b0\u578b\u7684\u73af\u5316\u7b56\u7565\u540c\u6837\u80fd\u591f\u826f\u597d\u5730\u5b9e\u73b0\u975e\u5bf9\u6620\u9009\u62e9\u6027\u4ee5\u53ca\u5bf9\u6620\u9009\u62e9\u6027\u7684\u63a7\u5236\uff0c\u8fdb\u800c\u83b7\u5f97\u4e00\u7cfb\u5217\u7ed3\u6784\u590d\u6742\u7684\u624b\u6027\u5206\u5b50\u3002<\/p>\n<blockquote><p>Palladium-Catalyzed Annulations of Strained Cyclic Allenes<br \/>\nA. V. Kelleghan, D. C. Witkowski, M. S. McVeigh, N. K. Garg, J. Am. Chem. Soc. 2021, 143, 9338. doi: <a href=\"https:\/\/pubs.acs.org\/doi\/10.1021\/jacs.1c04896\"><u>10.1021\/jacs.1c04896<\/u><\/a><u>.<\/u><\/p><\/blockquote>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/2-16.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-40102 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/2-16-680x122.png\" alt=\"\" width=\"680\" height=\"122\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/2-16-680x122.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/2-16-300x54.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/2-16-768x138.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/2-16.png 1082w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/a><\/p>\n<h4>\u6b63\u6587<\/h4>\n<p>\u81ea20\u4e16\u7eaa\u521d\u4ee5\u6765\uff0c\u77ac\u6001\u5f20\u529b\u73af\u4e2d\u95f4\u4f53 (transient strained cyclic intermediate) \u4f8b\u5982\u82ef\u7094 (<strong>1<\/strong>,\u00a0Figure 1A)\uff0c\u4e00\u76f4\u5907\u53d7\u5316\u5b66\u5bb6\u7684\u5e7f\u6cdb\u5173\u6ce8\u300220\u4e16\u7eaa\u521d\uff0c\u5728\u63d0\u51fa\u82ef\u7094\u4f5c\u4e3a\u53cd\u5e94\u6d3b\u6027\u4e2d\u95f4\u4f53\u7684\u5047\u8bbe\u4e4b\u540e\uff0c\u8fd9\u4e00\u4e2d\u95f4\u4f53\u7684\u5b58\u5728\uff0c\u4e00\u76f4\u4ee5\u6765\u5907\u53d7\u5b66\u672f\u754c\u7684\u4e89\u8bae\u3002\u7136\u800c\uff0c\u76f4\u523020\u4e16\u7eaa50\u5e74\u4ee3\uff0c\u901a\u8fc7Roberts<sup>[1]<\/sup>\u4e0eWittig<sup>[2<\/sup><sup>]-[<\/sup><sup>3]<\/sup>\u7684\u5f00\u521b\u6027\u5b9e\u9a8c\u7814\u7a76\uff0c\u8fdb\u800c\u8bc1\u5b9e\u8fd9\u4e00\u4e2d\u95f4\u4f53\u7684\u5b58\u5728\u3002\u7531\u4e8e\u82ef\u7094\u4e2d\u95f4\u4f53\u4e2d\u5b58\u5728\u9ad8\u5ea6\u7684\u73af\u5f20\u529b\uff0c\u56e0\u800c\uff0c\u80fd\u591f\u8868\u73b0\u51fa\u8f83\u4e3a\u72ec\u7279\u7684\u53cd\u5e94\u6d3b\u6027\u3002\u5e76\u4e14\uff0c\u901a\u8fc7\u82ef\u7094\u4e2d\u95f4\u4f53\u76f8\u5173\u7814\u7a76\u7684\u542f\u53d1\uff0c\u76ee\u524d\uff0c\u5df2\u7ecf\u6210\u529f\u8bbe\u8ba1\u51fa\u4e00\u7cfb\u5217\u76f8\u5173\u7684\u6742\u73af\u82b3\u7094\u4e2d\u95f4\u4f53\uff0c\u4f8b\u5982<strong>2<\/strong>\u4e0e<strong>3<\/strong>\uff0c\u4ee5\u53ca\u9971\u548c\u73af\u7094\u7c7b\u4f3c\u7269\uff0c\u4f8b\u5982\u73af\u5df1\u7094 <strong>4<\/strong>\u3002\u540c\u65f6\uff0c\u4e0a\u8ff0\u7684\u5f20\u529b\u73af\u7094\u4e2d\u95f4\u4f53\u5728\u5f53\u4ee3\u5408\u6210\u5de5\u5177\u7bb1 (modern synthetic toolbox)\u4e2d\u53d1\u6325\u6781\u4e3a\u91cd\u8981\u7684\u4f5c\u7528\uff0c\u76ee\u524d\uff0c\u5df2\u7ecf\u5e7f\u6cdb\u5e94\u7528\u4e8e\u6742\u73af\u3001\u50ac\u5316\u914d\u4f53\u3001\u5929\u7136\u4ea7\u7269\u3001\u519c\u7528\u5316\u5b66\u54c1\u4ee5\u53ca\u6709\u673a\u6750\u6599\u5206\u5b50\u7684\u6784\u5efa\u3002<\/p>\n<p>\u5c3d\u7ba1\u5f20\u529b\u73af\u7094\u4e2d\u95f4\u4f53\u7684\u7814\u7a76\uff0c\u76ee\u524d\u5df2\u7ecf\u53d7\u5230\u5408\u6210\u5316\u5b66\u5bb6\u7684\u5e7f\u6cdb\u5173\u6ce8\u3002\u7136\u800c\uff0c\u5bf9\u4e8e\u5177\u6709\u8f83\u9ad8\u73af\u5f20\u529b\u7684\u77ac\u6001\u73af\u8054\u70ef\u4e2d\u95f4\u4f53 (\u4f8b\u59821,2-\u73af\u5df1\u4e8c\u70ef<strong>5<\/strong>)\u00a0\u7684\u7814\u7a76\uff0c\u5219\u8f83\u5c11\u6709\u76f8\u5173\u7684\u6587\u732e\u62a5\u9053<sup>[<\/sup><sup>4]<\/sup>\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u5f20\u529b\u73af\u8054\u70ef\u4e0e\u5f20\u529b\u73af\u7094\u4e2d\u95f4\u4f53\u5177\u6709\u8f83\u4e3a\u76f8\u8fd1\u7684\u73af\u5f20\u529b\u4e0e\u53cd\u5e94\u6d3b\u6027<sup>[<\/sup><sup>5]<\/sup>\u3002\u5e76\u4e14\uff0c\u901a\u8fc7\u73af\u8054\u70ef\u4e2d\u95f4\u4f53\uff0c\u80fd\u591f\u987a\u5229\u5b9e\u73b0\u4e00\u7cfb\u5217\u5bcc\u542bsp<sup>3<\/sup>\u7acb\u4f53\u4e2d\u5fc3\u7684\u624b\u6027\u5206\u5b50\u4ee5\u53ca\u7acb\u4f53\u5316\u5b66\u66f4\u4e3a\u590d\u6742\u7684\u76f8\u5173\u6709\u673a\u5206\u5b50\u7684\u6784\u5efa<sup>[<\/sup><sup>6]<\/sup>\u3002\u7136\u800c\uff0c\u8fc4\u4eca\u4e3a\u6b62\uff0c\u4e0a\u8ff0\u4e2d\u95f4\u4f53\u76f8\u5173\u7684\u65b9\u6cd5\u5b66\u7814\u7a76\u4e3b\u8981\u6d89\u53ca\u4e09\u79cd\u4e0d\u540c\u7c7b\u578b\u7684\u5206\u5b50\u95f4\u53cd\u5e94\u8fc7\u7a0b (Figure\u00a01B)\uff0c\u5373\u4eb2\u6838\u6355\u83b7 (\u4f8b\u5982<strong>7<\/strong>+KO<em>t<\/em>-Bu\u2192<strong>6<\/strong>)\u3001\u73af\u52a0\u6210 (\u4f8b\u5982<strong>7<\/strong>+<strong>8<\/strong>\u2192<strong>9<\/strong>)\u4ee5\u53ca\u91c7\u7528\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u7684\u73af\u8054\u70ef\u6355\u83b7\u53cd\u5e94 (\u4f8b\u5982<strong>7<\/strong>+<strong>10<\/strong>\u2192<strong>11<\/strong>)<sup>[<\/sup><sup>7<\/sup><sup>]<\/sup><sup>-[8]<\/sup>\u3002\u7136\u800c\uff0c\u7531\u4e8e\u53cd\u5e94\u8fc7\u7a0b\u4e2d\uff0c\u9700\u8981\u4f7f\u4e24\u79cd\u8f83\u4f4e\u6d53\u5ea6\u7684\u6d3b\u6027\u4e2d\u95f4\u4f53\uff0c\u5373\u50ac\u5316\u4ea7\u751f\u7684\u4e2d\u95f4\u4f53\u4e0e\u539f\u4f4d\u5f62\u6210\u7684\u77ac\u6001\u73af\u8054\u70ef\u4e2d\u95f4\u4f53\uff0c\u4e4b\u95f4\u8fdb\u884c\u6709\u6548\u7684\u53cd\u5e94\uff0c\u56e0\u6b64\uff0c\u8fd9\u4e00\u7b56\u7565\u5177\u6709\u5176\u5185\u5728\u7684\u52a8\u529b\u5b66\u6311\u6218\u6027\u3002<\/p>\n<p>\u76ee\u524d\uff0c\u4ec5\u6709\u4e24\u4f8b\u6d89\u53ca\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u7684\uff0c\u5e76\u901a\u8fc7\u5f20\u529b\u73af\u8054\u70ef\u4e2d\u95f4\u4f53\u8fdb\u884c\u7684\u5408\u6210\u8f6c\u5316\u65b9\u6cd5\u5b66\u7684\u76f8\u5173\u7814\u7a76\u62a5\u9053\uff0c\u53732009\u5e74\uff0cGuiti\u00e1n\u7b49<sup>[<\/sup><sup>7<\/sup><sup>]<\/sup>\u62a5\u9053\u7684\u9996\u4f8bPd\u50ac\u5316\u7684\u73af\u8054\u70ef[2+2+2]\u53cd\u5e94\u65b9\u6cd5\u5b66\u4ee5\u53ca\u57282020\u5e74\uff0c\u672c\u8bfe\u9898\u7ec4<sup>[<\/sup><sup>8<\/sup><sup>]<\/sup>\u62a5\u9053\u7684\u91c7\u7528Ni\u50ac\u5316\u5242\u4fc3\u8fdb\u7684\u73af\u8054\u70ef\u4e0e\u82ef\u5e76\u4e09\u55ea (benzotriazinones)\u4e4b\u95f4\u7684\u73af\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u3002\u5e76\u4e14\uff0c\u901a\u8fc7\u4e0a\u8ff0\u7814\u7a76\u8868\u660e\uff0c\u9009\u62e9\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u4e0e\u73af\u8054\u70ef\u7684\u7ed3\u5408\uff0c\u80fd\u591f\u4e3a\u5f20\u529b\u4e2d\u95f4\u4f53\u5316\u5b66 (strained intermediate chemistry)\u7684\u7814\u7a76\u5f00\u8f9f\u51fa\u4e00\u6761\u5168\u65b0\u7684\u9014\u5f84\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/3-16.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-40103 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/3-16-680x600.png\" alt=\"\" width=\"680\" height=\"600\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/3-16-680x600.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/3-16-300x265.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/3-16.png 738w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/a><\/p>\n<p>\u53d7\u5230\u4e0a\u8ff0\u7814\u7a76\u62a5\u9053\u7684\u542f\u53d1\uff0c\u4f5c\u8005\u8bbe\u8ba1\u51fa\u4e00\u79cd\u5168\u65b0\u7684\u901a\u8fc7\u5f20\u529b\u73af\u8054\u70ef\u53c2\u4e0e\u7684\u73af\u5316\u53cd\u5e94\u7b56\u7565 (Scheme 1)\u3002\u4f5c\u8005\u8bbe\u60f3\uff0c\u9996\u5148\uff0c\u901a\u8fc7\u5177\u6709\u82b3\u57fa\u7898\u4ee5\u53ca\u4eb2\u6838\u6027XH\u7ed3\u6784\u5355\u5143\u7684\u53cc\u529f\u80fd\u73af\u5316\u53c2\u4e0e\u7269<strong>12<\/strong>\u4e0e\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u5242\u4e4b\u95f4\u7684\u6c27\u5316\u52a0\u6210\u8fc7\u7a0b\uff0c\u5f62\u6210\u4e2d\u95f4\u4f53<strong>15<\/strong>\u3002\u540c\u65f6\uff0c\u7845\u57fa\u4e09\u6c1f\u7532\u78fa\u9178\u916f<strong>13<\/strong>\u901a\u8fc7\u6c1f\u79bb\u5b50\u4fc3\u8fdb\u7684\u53bb\u7845\u57fa\u5316\u8fc7\u7a0b\uff0c\u539f\u4f4d\u5f62\u6210\u5f20\u529b\u73af\u8054\u70ef\u4e2d\u95f4\u4f53<strong>7<\/strong>\u3002\u4e4b\u540e\uff0c\u901a\u8fc7\u73af\u8054\u70ef\u4e2d\u95f4\u4f53<strong>7<\/strong>\u4e0e<strong>15<\/strong>\u4e2dAr-M\u952e\u7684\u8fc1\u79fb\u63d2\u5165\u8fc7\u7a0b\uff0c\u5f62\u6210<em>\u03b7<\/em><sup>3<\/sup>-\u914d\u5408\u7269<strong>16<\/strong>\u3002\u63a5\u4e0b\u6765\uff0c\u901a\u8fc7\u914d\u5408\u7269<strong>16<\/strong>\u8fdb\u884c\u540e\u7eed\u7684\u4eb2\u6838\u73af\u5316\u4e0e\u8fd8\u539f\u6d88\u9664\u8fc7\u7a0b\uff0c\u5373\u53ef\u83b7\u5f97\u76f8\u5e94\u7684\u4e09\u73af\u4ea7\u7269<strong>14<\/strong>\u3002\u57fa\u4e8e\u4e0a\u8ff0\u7684\u7814\u7a76\u8bbe\u60f3\uff0c\u8fd9\u91cc\uff0c\u672c\u8bfe\u9898\u7ec4\u6210\u529f\u5f00\u53d1\u51fa\u4e00\u79cd\u5728\u94af\u50ac\u5316\u5242\u5b58\u5728\u7684\u6761\u4ef6\u4e0b\uff0c\u901a\u8fc7\u539f\u4f4d\u5f62\u6210\u7684\u5f20\u529b\u73af\u8054\u70ef\u4e2d\u95f4\u4f53\u53c2\u4e0e\u7684\u73af\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u3002\u5e76\u901a\u8fc7\u8fd9\u4e00\u5168\u65b0\u7684\u73af\u5316\u53cd\u5e94\u7b56\u7565\uff0c\u6210\u529f\u5b9e\u73b0\u4e00\u7cfb\u5217\u7a20\u5408\u591a\u73af\u5206\u5b50\u7684\u6784\u5efa\u3002\u540c\u65f6\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u53d1\u73b0\uff0c\u8fd9\u4e00\u5168\u65b0\u7684\u73af\u5316\u7b56\u7565\u540c\u6837\u80fd\u591f\u6709\u6548\u5730\u5b9e\u73b0\u4f18\u826f\u7684\u7acb\u4f53\u9009\u62e9\u6027\u4e0e\u5bf9\u6620\u9009\u62e9\u6027\u7684\u63a7\u5236\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/4-16.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-40104 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/4-16-680x461.png\" alt=\"\" width=\"680\" height=\"461\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/4-16-680x461.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/4-16-300x203.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/4-16.png 748w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/a><\/p>\n<p>\u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528\u90bb\u7898\u82ef\u80fa\u884d\u751f\u7269<strong>17<\/strong>\u4e0e\u7845\u57fa\u4e09\u6c1f\u7532\u78fa\u9178\u916f\u884d\u751f\u7269<strong>18<\/strong>\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u76f8\u5173\u73af\u5316\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u7b5b\u9009 (Table 1)\u3002\u8fdb\u800c\u786e\u5b9a\u6700\u4f73\u7684\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u91c7\u7528Pd(OAc)<sub>2<\/sub>\u4f5c\u4e3a\u50ac\u5316\u5242\uff0cDavePhos\u4f5c\u4e3a\u914d\u4f53\uff0cDMF\u4f5c\u4e3a\u53cd\u5e94\u6eb6\u5242\uff0cBu<sub>4<\/sub>NOTf\u4e0eCsF\u4f5c\u4e3a\u6dfb\u52a0\u5242\u4ee5\u53caNa<sub>2<\/sub>CO<sub>3<\/sub>\u4f5c\u4e3a\u78b1\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a80 <sup>o<\/sup>C\uff0c\u6700\u7ec8\u83b7\u5f9797%\u6536\u7387\u7684\u76ee\u6807\u4ea7\u7269<strong>19a<\/strong>\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/5-11.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-40105 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/5-11-680x556.png\" alt=\"\" width=\"680\" height=\"556\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/5-11-680x556.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/5-11-300x245.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/5-11.png 744w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/a><\/p>\n<p>\u5728\u83b7\u5f97\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e4b\u540e\uff0c\u4f5c\u8005\u5f00\u59cb\u5bf9\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u7684\u5e95\u7269\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u7814\u7a76 (Figure 2)\u3002\u9996\u5148\uff0c\u8be5\u5c0f\u7ec4\u53d1\u73b0\uff0c\u90bb\u7898\u82ef\u80fa\u884d\u751f\u7269\u4e2d\u7684<em>N<\/em><em>&#8211;<\/em>\u53d6\u4ee3\u57fa\u4e3a-Ts\u3001-Boc\u4ee5\u53ca-Ac\u65f6\uff0c\u5747\u80fd\u591f\u987a\u5229\u5730\u53c2\u4e0e\u4e0a\u8ff0\u7684\u73af\u5316\u8fc7\u7a0b\uff0c\u5e76\u83b7\u5f97\u76f8\u5e94\u7684\u73af\u5316\u4ea7\u7269<strong>19a<\/strong>&#8211;<strong>19c<\/strong>\u3002\u540c\u65f6\uff0c\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\uff0c\u5bf9\u4e8e\u90bb\u7898\u82ef\u80fa\u5e95\u7269\u82ef\u57fa\u4e2d\u5b58\u5728\u7684\u4e00\u7cfb\u5217\u7535\u5b50\u4e0e\u7acb\u4f53\u6548\u5e94\u4e0d\u540c\u7684\u53d6\u4ee3\u57fa\u56e2\uff0c\u5747\u80fd\u591f\u826f\u597d\u5730\u517c\u5bb9\uff0c\u5e76\u83b7\u5f97\u76f8\u5e94\u7684\u56db\u6c22\u5494\u5511\u4ea7\u7269<strong>22<\/strong>&#8211;<strong>3<\/strong><strong>0<\/strong>\u3002\u540c\u65f6\uff0c\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u8868\u73b0\u51fa\u4f18\u826f\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u3002\u4e4b\u540e\uff0c\u8be5\u5c0f\u7ec4\u8fdb\u4e00\u6b65\u5bf9\u5404\u7c7b\u6742\u73af\u5e95\u7269\u4ee5\u53ca\u6742\u73af\u8054\u70ef\u524d\u4f53\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76\u3002\u5b9e\u9a8c\u8868\u660e\uff0c\u5177\u6709\u6eb4\u5421\u5576\u57fa\u4ee5\u53ca\u7898\u5421\u5576\u57fa\u7684\u6742\u73af\u5e95\u7269\u540c\u6837\u80fd\u591f\u7ecf\u5386\u9884\u671f\u7684\u73af\u5316\u8fc7\u7a0b\uff0c\u5e76\u4ee5\u826f\u597d\u81f3\u4f18\u826f\u7684\u53cd\u5e94\u6536\u7387\u83b7\u5f97\u76f8\u5e94\u76ee\u6807\u4ea7\u7269<strong>31<\/strong>\u3002\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u4f5c\u4e3a\u73af\u8054\u70ef\u524d\u4f53\u7684\u7845\u57fa\u4e09\u6c1f\u7532\u78fa\u9178\u916f<strong><b>1<\/b><\/strong><strong><b>3<\/b><\/strong>\u7684\u76f8\u5e94\u6c27\u6742\u4e0e\u6c2e\u6742\u884d\u751f\u7269\uff0c\u5747\u80fd\u591f\u8f83\u597d\u5730\u4e0e\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u4f53\u7cfb\u517c\u5bb9\uff0c\u5e76\u83b7\u5f97\u76f8\u5e94\u7684\u76ee\u6807\u4ea7\u7269<strong>32<\/strong>&#8211;<strong>3<\/strong><strong>3<\/strong>\u3002\u5e76\u4e14\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u89c2\u5bdf\u5230\uff0c\u4e03\u5143\u73af\u8054\u70ef\u524d\u4f53\u540c\u6837\u80fd\u591f\u987a\u5229\u5730\u53c2\u4e0e\u4e0a\u8ff0\u7684\u73af\u5316\u8fc7\u7a0b\uff0c\u5e76\u83b7\u5f97\u76f8\u5e94\u7684\u6742\u73af\u4ea7\u7269<strong>3<\/strong><strong>4<\/strong>\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/6-9.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-40106 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/6-9-622x1024.png\" alt=\"\" width=\"622\" height=\"1024\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/6-9-622x1024.png 622w, https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/6-9-182x300.png 182w, https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/6-9-768x1265.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/6-9-932x1536.png 932w, https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/6-9.png 953w\" sizes=\"(max-width: 622px) 100vw, 622px\" \/><\/a><\/p>\n<p>\u4e4b\u540e\uff0c\u4f5c\u8005\u5bf9\u8fdb\u4e00\u6b65\u5176\u5b83\u4e0d\u540c\u7c7b\u578b\u7684\u524d\u4eb2\u6838\u5e95\u7269\u8fdb\u884c\u6df1\u5165\u7814\u7a76 (Figure 3)\u3002\u5b9e\u9a8c\u8868\u660e\uff0c<em><i>O<\/i><\/em>-\u524d\u4eb2\u6838\u5e95\u7269 <strong>35<\/strong>\u4e0e<strong>37<\/strong>\u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u5206\u522b\u80fd\u591f\u83b7\u5f97\u76f8\u5e94\u7684\u73af\u5316\u4ea7\u7269<strong>36<\/strong><strong>\u00a0<\/strong>(87%\u53cd\u5e94\u6536\u7387)\u4e0e<strong>38<\/strong><strong>\u00a0<\/strong>(46%\u53cd\u5e94\u6536\u7387)\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u9009\u62e9Xantphos\u4f5c\u4e3a\u914d\u4f53\u65f6\uff0c\u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u91c7\u7528<em><i>N<\/i><\/em>-\u524d\u4eb2\u6838\u5e95\u7269 (<strong>39<\/strong>)\uff0c\u540c\u6837\u80fd\u591f\u83b7\u5f9771%\u6536\u7387\u7684\u76ee\u6807\u4ea7\u7269<strong>40<\/strong>\u3002\u63a5\u4e0b\u6765\uff0c\u8be5\u5c0f\u7ec4\u89c2\u5bdf\u5230\uff0c\u78b3\u57fa\u524d\u4eb2\u6838\u5e95\u7269(C-base pronucleophile)\u00a0<strong>41<\/strong>\u5728\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u540c\u6837\u80fd\u591f\u83b7\u5f9760%\u6536\u7387\u7684\u5177\u6709\u56db\u7ea7\u78b3\u4e2d\u5fc3\u7684\u56db\u6c22\u82b4\u5206\u5b50<strong>42<\/strong>\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/7-9.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-40107 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/7-9-680x513.png\" alt=\"\" width=\"680\" height=\"513\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/7-9-680x513.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/7-9-300x226.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/7-9.png 750w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/a><\/p>\n<p>\u6b64\u5916\uff0c\u4f5c\u8005\u540c\u6837\u5bf9\u4e0a\u8ff0\u73af\u5316\u8fc7\u7a0b\u4e2d\u7684\u975e\u5bf9\u6620\u4e0e\u5bf9\u6620\u9009\u62e9\u6027\u7684\u63a7\u5236\uff0c\u8fdb\u884c\u6df1\u5165\u8003\u5bdf (Figure 4)\u3002\u9996\u5148\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u4e09\u7ea7\u82c4\u9187<strong>43<\/strong>\u80fd\u591f\u4e0e\u8054\u70ef\u524d\u4f53<strong>18<\/strong>\u5728\u4e0a\u8ff0\u7684\u6807\u51c6\u73af\u5316\u6761\u4ef6\u4e0b\u8fdb\u884c\u53cd\u5e94\uff0c\u5e76\u83b7\u5f97\u76f8\u5e94\u7684\u56db\u73af\u4ea7\u7269<strong>44<\/strong><strong>\u00a0<\/strong>(5.6:1 d.r.)\u3002\u4e4b\u540e\uff0c\u8be5\u5c0f\u7ec4\u9009\u62e9\u7898\u5421\u5576<strong>45<\/strong>\u4e0e\u8054\u70ef\u524d\u4f53<strong>46<\/strong>\u5728Pd<sub>2<\/sub>(dba)<sub>3<\/sub>\/Mandyphos\u50ac\u5316\u5242\u4f53\u7cfb\u4e2d\u8fdb\u884c\u53cd\u5e94\uff0c\u6700\u7ec8\u83b7\u5f9790%\u00a0ee\u7684\u4e09\u73af\u4ea7\u7269 (-)-<strong>47<\/strong>\u3002\u5e76\u4e14\uff0c\u8be5\u5c0f\u7ec4\u53d1\u73b0\uff0c\u4e09\u73af\u4ea7\u7269(-)-<strong>47<\/strong>\u80fd\u591f\u7ee7\u7eed\u4e0e\u6c27\u6742\u8054\u70ef\u524d\u4f53 (oxacyclic allene precursor)<strong>48<\/strong>\u8fdb\u884c\u53cd\u5e94\uff0c\u8fdb\u800c\u83b7\u5f97\u76f8\u5e94\u4ea7\u7269(+)-<strong>49<\/strong>\u3002\u4e4b\u540e\uff0c(+)-<strong>49<\/strong>\u4e2d\u7684\u70ef\u57fa\u7ed3\u6784\u5355\u5143\u8fdb\u4e00\u6b65\u7ecf\u5386\u7acb\u4f53\u9009\u62e9\u6027\u6027\u7684\u73af\u6c27\u5316\u8fc7\u7a0b\uff0c\u6700\u7ec8\u83b7\u5f97\u5bf9\u6620\u5bcc\u96c6\u7684\u516d\u73af\u5206\u5b50 (+)-<strong>50<\/strong>\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/8-7.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-40108 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/8-7.png\" alt=\"\" width=\"652\" height=\"640\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/8-7.png 652w, https:\/\/assets.www.gsbet888.com\/uploads\/2021\/09\/8-7-300x294.png 300w\" sizes=\"(max-width: 652px) 100vw, 652px\" \/><\/a><\/p>\n<h4>\u603b\u7ed3<\/h4>\n<p>California\u5927\u5b66\u7684N. K. Garg\u6559\u6388\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5728\u94af\u50ac\u5316\u6761\u4ef6\u4e0b\uff0c\u901a\u8fc7\u539f\u4f4d\u5f62\u6210\u7684\u5f20\u529b\u73af\u8054\u70ef\u4e2d\u95f4\u4f53\u8fdb\u884c\u7684\u73af\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u5176\u4e2d\u91c7\u7528\u82b3\u5364\u4e0e\u73af\u8054\u70ef\u524d\u4f53\u4f5c\u4e3a\u53cd\u5e94\u5e95\u7269\uff0c\u8fdb\u800c\u6210\u529f\u5b8c\u6210\u4e00\u7cfb\u5217\u7a20\u6742\u73af\u5206\u5b50\u7684\u6784\u5efa\u3002\u540c\u65f6\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u5bf9\u4e0a\u8ff0\u73af\u5316\u7b56\u7565\u4e2d\u975e\u5bf9\u6620\u9009\u62e9\u6027\u4e0e\u5bf9\u6620\u9009\u62e9\u6027\u7684\u63a7\u5236\u8fdb\u884c\u6df1\u5165\u7814\u7a76\uff0c\u5e76\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u7269<strong>44<\/strong>\u4e0e(-)-<strong>47<\/strong>\u3002\u6b64\u5916\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u901a\u8fc7(-)-<strong>47<\/strong>\u4f5c\u4e3a\u5173\u952e\u780c\u5757\uff0c\u80fd\u591f\u8fdb\u4e00\u6b65\u83b7\u5f97\u5bf9\u6620\u5bcc\u96c6\u7684\u516d\u73af\u5206\u5b50 (+)-<strong>50<\/strong>\u3002<\/p>\n<h4><strong><b>\u53c2\u8003\u6587\u732e<\/b><\/strong><\/h4>\n[1]\u00a0J. D. Roberts, H. E. Simmons, L. A. Carlsmith, C. W.\u00a0Vaughan,\u00a0<em>J. Am. Chem. Soc. <\/em><strong>1953<\/strong>, <em>75<\/em>, 3290.\u00a0doi:\u00a0<a href=\"https:\/\/doi.org\/10.1021\/ja01109a523\"><u>10.1021\/ja01109a523<\/u><\/a><u>.<\/u><\/p>\n[2]\u00a0G. Wittig, <em>Naturwissenschaften<\/em>\u00a0<strong>1942<\/strong>, <em>30<\/em>, 696.\u00a0doi:\u00a0<a href=\"https:\/\/link.springer.com\/article\/10.1007\/BF01489519\"><u>10.1007\/BF01489519<\/u><\/a><u>.<\/u><\/p>\n[3]\u00a0G. Wittig, L. Pohmer, <em>Angew. Chem.<\/em>\u00a0<strong>1955<\/strong>, <em>67<\/em>, 348.\u00a0doi:\u00a0<a href=\"https:\/\/doi.org\/10.1002\/ange.19550671306\"><u>10.1002\/ange.19550671306<\/u><\/a><u>.<\/u><\/p>\n[4]\u00a0M. Christl, <a href=\"https:\/\/sci-hub.se\/10.1002\/9783527619573.ch6\"><u>Cyclic allenes up to seven-membered rings<\/u><\/a>. Modern\u00a0Allene Chemistry, N. Krause, S. A. K. Kashmi Eds. Wiley-VCH:\u00a0Weinheim, <strong><b>2004<\/b><\/strong>, 243.<\/p>\n[5]\u00a0G. Wittig, P. Fritze, <em><i>Angew. Chem. Int. Ed.<\/i><\/em>\u00a0<strong><b>1966<\/b><\/strong>, <em><i>5<\/i><\/em>, 846. doi:\u00a0<a href=\"https:\/\/doi.org\/10.1002\/anie.196608461\"><u>10.1002\/anie.196608461<\/u><\/a><u>.<\/u><\/p>\n[6]\u00a0F. Lovering, J. Bikker, C. Humblet, <em><i>J.<\/i><\/em><em><i>\u00a0<\/i><\/em><em><i>Med. Chem.<\/i><\/em><strong><em><b><i>\u00a0<\/i><\/b><\/em><\/strong><strong><b>2009<\/b><\/strong>,<em><i>\u00a052<\/i><\/em>, 6752. doi:\u00a0<a href=\"https:\/\/doi.org\/10.1021\/jm901241e\"><u>10.1021\/jm901241e<\/u><\/a><u>.<\/u><\/p>\n[7] I. Quintana, D. Pe\u00f1a, D. P\u00e9rez, E. Guiti\u00e1n, <em>Eur. J.<\/em><em>\u00a0<\/em><em>Org. Chem.<\/em>\u00a0<strong>2009<\/strong>, 5519.\u00a0doi:\u00a0<a href=\"https:\/\/doi.org\/10.1002\/ejoc.200900631\"><u>10.1002\/ejoc.200900631<\/u><\/a><u>.<\/u><\/p>\n[8]\u00a0M. M. Yamano, A. V. Kelleghan, Q. Shao, M.\u00a0Giroud, B. J. Simmons, B. Li, S. Chen, K. N. Houk, N. K. Garg, <em>Nature<\/em>\u00a0<strong>2020<\/strong>,\u00a0<em>586<\/em>, 242.\u00a0doi:\u00a0<a href=\"#citeas\"><u>10.1038\/s41586-020-2701-2<\/u><\/a><u>.<\/u><\/p>\n<p>&nbsp;<\/p>\n<p><strong>\u672c\u6587\u7248\u6743\u5c5e\u4e8e\u00a0<a href=\"\/\/www.gsbet888.com\/\">Chem-Station\u5316\u5b66\u7a7a\u95f4<\/a>\uff0c \u6b22\u8fce\u70b9\u51fb\u6309\u94ae\u5206\u4eab\uff0c\u672a\u7ecf\u8bb8\u53ef\uff0c\u8c22\u7edd\u8f6c\u8f7d\uff01<\/strong><\/p>\n","protected":false},"excerpt":{"rendered":"\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749 \u5bfc\u8bfb \u8fd1\u65e5\uff0cCalifornia\u5927\u5b66\u7684N.\u00a0K. Garg\u6559\u6388\u8bfe\u9898\u7ec4\u5728JACS\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u5728\u94af\u50ac\u5316\u6761\u4ef6\u4e0b\uff0c\u901a\u8fc7\u539f\u4f4d\u5f62\u6210\u7684\u5f20\u529b\u73af\u8054\u70ef (strained cyclic allene)\u00a0\u53c2\u4e0e\u7684\u73af\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u3002\u8fd9\u4e00\u5168\u65b0\u7684\u73af\u5316\u7b56\u7565\u4e2d\u91c7\u7528\u82b3\u5364\u4e0e\u73af\u8054\u70ef\u524d\u4f53\uff0c\u4f5c\u4e3a\u53cd\u5e94\u53c2\u4e0e\u7269\uff0c\u8fdb\u800c\u6210\u529f\u5b8c\u6210\u4e00\u7cfb\u5217\u7a20\u6742\u73af\u5206\u5b50\u7684\u6784\u5efa\u3002\u540c\u65f6\uff0c\u4e0a\u8ff0\u7684\u73af\u5316\u8fc7\u7a0b\u4e2d\u6d89\u53ca\u4e24\u79cd\u4e0d\u540c\u7684\u65b0\u952e\u4ee5\u53ca\u4e00\u4e2asp3\u4e2d\u5fc3\u7684\u5f62\u6210\u3002\u6b64\u5916\uff0c\u8fd9\u4e00\u65b0\u578b\u7684\u73af\u5316\u7b56\u7565\u540c\u6837\u80fd\u591f\u826f\u597d\u5730\u5b9e\u73b0\u975e\u5bf9\u6620\u9009\u62e9\u6027\u4ee5\u53ca\u5bf9\u6620\u9009\u62e9\u6027\u7684\u63a7\u5236\uff0c\u8fdb\u800c\u83b7\u5f97\u4e00\u7cfb\u5217\u7ed3\u6784\u590d\u6742\u7684\u624b\u6027\u5206\u5b50\u3002 Palladium-Catalyzed Annulations of Strained Cyclic Allenes A. V. Kelleghan, D. C. Witkowski, M. S. McVeigh, N. K. Garg, J. Am. Chem. Soc. 2021, 143, 9338. doi: 10.1021\/jacs.1c04896. \u6b63\u6587 \u81ea20\u4e16\u7eaa\u521d\u4ee5\u6765\uff0c\u77ac\u6001\u5f20\u529b\u73af\u4e2d\u95f4\u4f53 (transient strained cyclic intermediate) \u4f8b\u5982\u82ef\u7094 (1,\u00a0Figure 1A)\uff0c\u4e00\u76f4\u5907\u53d7\u5316\u5b66\u5bb6\u7684\u5e7f\u6cdb\u5173\u6ce8\u300220\u4e16\u7eaa\u521d\uff0c\u5728\u63d0\u51fa\u82ef\u7094\u4f5c\u4e3a\u53cd\u5e94\u6d3b\u6027\u4e2d\u95f4\u4f53\u7684\u5047\u8bbe\u4e4b\u540e\uff0c\u8fd9\u4e00\u4e2d\u95f4\u4f53\u7684\u5b58\u5728\uff0c\u4e00\u76f4\u4ee5\u6765\u5907\u53d7\u5b66\u672f\u754c\u7684\u4e89\u8bae\u3002\u7136\u800c\uff0c\u76f4\u523020\u4e16\u7eaa50\u5e74\u4ee3\uff0c\u901a\u8fc7Roberts[1]\u4e0eWittig[2]-[3]\u7684\u5f00\u521b\u6027\u5b9e\u9a8c\u7814\u7a76\uff0c\u8fdb\u800c\u8bc1\u5b9e\u8fd9\u4e00\u4e2d\u95f4\u4f53\u7684\u5b58\u5728\u3002\u7531\u4e8e\u82ef\u7094\u4e2d\u95f4\u4f53\u4e2d\u5b58\u5728\u9ad8\u5ea6\u7684\u73af\u5f20\u529b\uff0c\u56e0\u800c\uff0c\u80fd\u591f\u8868\u73b0\u51fa\u8f83\u4e3a\u72ec\u7279\u7684\u53cd\u5e94\u6d3b\u6027\u3002\u5e76\u4e14\uff0c\u901a\u8fc7\u82ef\u7094\u4e2d\u95f4\u4f53\u76f8\u5173\u7814\u7a76\u7684\u542f\u53d1\uff0c\u76ee\u524d\uff0c\u5df2\u7ecf\u6210\u529f\u8bbe\u8ba1\u51fa\u4e00\u7cfb\u5217\u76f8\u5173\u7684\u6742\u73af\u82b3\u7094\u4e2d\u95f4\u4f53\uff0c\u4f8b\u59822\u4e0e3\uff0c\u4ee5\u53ca\u9971\u548c\u73af\u7094\u7c7b\u4f3c\u7269\uff0c\u4f8b\u5982\u73af\u5df1\u7094 4\u3002\u540c\u65f6\uff0c\u4e0a\u8ff0\u7684\u5f20\u529b\u73af\u7094\u4e2d\u95f4\u4f53\u5728\u5f53\u4ee3\u5408\u6210\u5de5\u5177\u7bb1 (modern synthetic toolbox)\u4e2d\u53d1\u6325\u6781\u4e3a\u91cd\u8981\u7684\u4f5c\u7528\uff0c\u76ee\u524d\uff0c\u5df2\u7ecf\u5e7f\u6cdb\u5e94\u7528\u4e8e\u6742\u73af\u3001\u50ac\u5316\u914d\u4f53\u3001\u5929\u7136\u4ea7\u7269\u3001\u519c\u7528\u5316\u5b66\u54c1\u4ee5\u53ca\u6709\u673a\u6750\u6599\u5206\u5b50\u7684\u6784\u5efa\u3002 \u5c3d\u7ba1\u5f20\u529b\u73af\u7094\u4e2d\u95f4\u4f53\u7684\u7814\u7a76\uff0c\u76ee\u524d\u5df2\u7ecf\u53d7\u5230\u5408\u6210\u5316\u5b66\u5bb6\u7684\u5e7f\u6cdb\u5173\u6ce8\u3002\u7136\u800c\uff0c\u5bf9\u4e8e\u5177\u6709\u8f83\u9ad8\u73af\u5f20\u529b\u7684\u77ac\u6001\u73af\u8054\u70ef\u4e2d\u95f4\u4f53 (\u4f8b\u59821,2-\u73af\u5df1\u4e8c\u70ef5)\u00a0\u7684\u7814\u7a76\uff0c\u5219\u8f83\u5c11\u6709\u76f8\u5173\u7684\u6587\u732e\u62a5\u9053[4]\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u5f20\u529b\u73af\u8054\u70ef\u4e0e\u5f20\u529b\u73af\u7094\u4e2d\u95f4\u4f53\u5177\u6709\u8f83\u4e3a\u76f8\u8fd1\u7684\u73af\u5f20\u529b\u4e0e\u53cd\u5e94\u6d3b\u6027[5]\u3002\u5e76\u4e14\uff0c\u901a\u8fc7\u73af\u8054\u70ef\u4e2d\u95f4\u4f53\uff0c\u80fd\u591f\u987a\u5229\u5b9e\u73b0\u4e00\u7cfb\u5217\u5bcc\u542bsp3\u7acb\u4f53\u4e2d\u5fc3\u7684\u624b\u6027\u5206\u5b50\u4ee5\u53ca\u7acb\u4f53\u5316\u5b66\u66f4\u4e3a\u590d\u6742\u7684\u76f8\u5173\u6709\u673a\u5206\u5b50\u7684\u6784\u5efa[6]\u3002\u7136\u800c\uff0c\u8fc4\u4eca\u4e3a\u6b62\uff0c\u4e0a\u8ff0\u4e2d\u95f4\u4f53\u76f8\u5173\u7684\u65b9\u6cd5\u5b66\u7814\u7a76\u4e3b\u8981\u6d89\u53ca\u4e09\u79cd\u4e0d\u540c\u7c7b\u578b\u7684\u5206\u5b50\u95f4\u53cd\u5e94\u8fc7\u7a0b (Figure\u00a01B)\uff0c\u5373\u4eb2\u6838\u6355\u83b7 (\u4f8b\u59827+KOt-Bu\u21926)\u3001\u73af\u52a0\u6210 (\u4f8b\u59827+8\u21929)\u4ee5\u53ca\u91c7\u7528\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u7684\u73af\u8054\u70ef\u6355\u83b7\u53cd\u5e94 (\u4f8b\u59827+10\u219211)[7]-[8]\u3002\u7136\u800c\uff0c\u7531\u4e8e\u53cd\u5e94\u8fc7\u7a0b\u4e2d\uff0c\u9700\u8981\u4f7f\u4e24\u79cd\u8f83\u4f4e\u6d53\u5ea6\u7684\u6d3b\u6027\u4e2d\u95f4\u4f53\uff0c\u5373\u50ac\u5316\u4ea7\u751f\u7684\u4e2d\u95f4\u4f53\u4e0e\u539f\u4f4d\u5f62\u6210\u7684\u77ac\u6001\u73af\u8054\u70ef\u4e2d\u95f4\u4f53\uff0c\u4e4b\u95f4\u8fdb\u884c\u6709\u6548\u7684\u53cd\u5e94\uff0c\u56e0\u6b64\uff0c\u8fd9\u4e00\u7b56\u7565\u5177\u6709\u5176\u5185\u5728\u7684\u52a8\u529b\u5b66\u6311\u6218\u6027\u3002 \u76ee\u524d\uff0c\u4ec5\u6709\u4e24\u4f8b\u6d89\u53ca\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u7684\uff0c\u5e76\u901a\u8fc7\u5f20\u529b\u73af\u8054\u70ef\u4e2d\u95f4\u4f53\u8fdb\u884c\u7684\u5408\u6210\u8f6c\u5316\u65b9\u6cd5\u5b66\u7684\u76f8\u5173\u7814\u7a76\u62a5\u9053\uff0c\u53732009\u5e74\uff0cGuiti\u00e1n\u7b49[7]\u62a5\u9053\u7684\u9996\u4f8bPd\u50ac\u5316\u7684\u73af\u8054\u70ef[2+2+2]\u53cd\u5e94\u65b9\u6cd5\u5b66\u4ee5\u53ca\u57282020\u5e74\uff0c\u672c\u8bfe\u9898\u7ec4[8]\u62a5\u9053\u7684\u91c7\u7528Ni\u50ac\u5316\u5242\u4fc3\u8fdb\u7684\u73af\u8054\u70ef\u4e0e\u82ef\u5e76\u4e09\u55ea (benzotriazinones)\u4e4b\u95f4\u7684\u73af\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u3002\u5e76\u4e14\uff0c\u901a\u8fc7\u4e0a\u8ff0\u7814\u7a76\u8868\u660e\uff0c\u9009\u62e9\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u4e0e\u73af\u8054\u70ef\u7684\u7ed3\u5408\uff0c\u80fd\u591f\u4e3a\u5f20\u529b\u4e2d\u95f4\u4f53\u5316\u5b66 (strained intermediate chemistry)\u7684\u7814\u7a76\u5f00\u8f9f\u51fa\u4e00\u6761\u5168\u65b0\u7684\u9014\u5f84\u3002 \u53d7\u5230\u4e0a\u8ff0\u7814\u7a76\u62a5\u9053\u7684\u542f\u53d1\uff0c\u4f5c\u8005\u8bbe\u8ba1\u51fa\u4e00\u79cd\u5168\u65b0\u7684\u901a\u8fc7\u5f20\u529b\u73af\u8054\u70ef\u53c2\u4e0e\u7684\u73af\u5316\u53cd\u5e94\u7b56\u7565 (Scheme 1)\u3002\u4f5c\u8005\u8bbe\u60f3\uff0c\u9996\u5148\uff0c\u901a\u8fc7\u5177\u6709\u82b3\u57fa\u7898\u4ee5\u53ca\u4eb2\u6838\u6027XH\u7ed3\u6784\u5355\u5143\u7684\u53cc\u529f\u80fd\u73af\u5316\u53c2\u4e0e\u726912\u4e0e\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u5242\u4e4b\u95f4\u7684\u6c27\u5316\u52a0\u6210\u8fc7\u7a0b\uff0c\u5f62\u6210\u4e2d\u95f4\u4f5315\u3002\u540c\u65f6\uff0c\u7845\u57fa\u4e09\u6c1f\u7532\u78fa\u9178\u916f13\u901a\u8fc7\u6c1f\u79bb\u5b50\u4fc3\u8fdb\u7684\u53bb\u7845\u57fa\u5316\u8fc7\u7a0b\uff0c\u539f\u4f4d\u5f62\u6210\u5f20\u529b\u73af\u8054\u70ef\u4e2d\u95f4\u4f537\u3002\u4e4b\u540e\uff0c\u901a\u8fc7\u73af\u8054\u70ef\u4e2d\u95f4\u4f537\u4e0e15\u4e2dAr-M\u952e\u7684\u8fc1\u79fb\u63d2\u5165\u8fc7\u7a0b\uff0c\u5f62\u6210\u03b73-\u914d\u5408\u726916\u3002\u63a5\u4e0b\u6765\uff0c\u901a\u8fc7\u914d\u5408\u726916\u8fdb\u884c\u540e\u7eed\u7684\u4eb2\u6838\u73af\u5316\u4e0e\u8fd8\u539f\u6d88\u9664\u8fc7\u7a0b\uff0c\u5373\u53ef\u83b7\u5f97\u76f8\u5e94\u7684\u4e09\u73af\u4ea7\u726914\u3002\u57fa\u4e8e\u4e0a\u8ff0\u7684\u7814\u7a76\u8bbe\u60f3\uff0c\u8fd9\u91cc\uff0c\u672c\u8bfe\u9898\u7ec4\u6210\u529f\u5f00\u53d1\u51fa\u4e00\u79cd\u5728\u94af\u50ac\u5316\u5242\u5b58\u5728\u7684\u6761\u4ef6\u4e0b\uff0c\u901a\u8fc7\u539f\u4f4d\u5f62\u6210\u7684\u5f20\u529b\u73af\u8054\u70ef\u4e2d\u95f4\u4f53\u53c2\u4e0e\u7684\u73af\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u3002\u5e76\u901a\u8fc7\u8fd9\u4e00\u5168\u65b0\u7684\u73af\u5316\u53cd\u5e94\u7b56\u7565\uff0c\u6210\u529f\u5b9e\u73b0\u4e00\u7cfb\u5217\u7a20\u5408\u591a\u73af\u5206\u5b50\u7684\u6784\u5efa\u3002\u540c\u65f6\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u53d1\u73b0\uff0c\u8fd9\u4e00\u5168\u65b0\u7684\u73af\u5316\u7b56\u7565\u540c\u6837\u80fd\u591f\u6709\u6548\u5730\u5b9e\u73b0\u4f18\u826f\u7684\u7acb\u4f53\u9009\u62e9\u6027\u4e0e\u5bf9\u6620\u9009\u62e9\u6027\u7684\u63a7\u5236\u3002 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2)\u3002\u9996\u5148\uff0c\u8be5\u5c0f\u7ec4\u53d1\u73b0\uff0c\u90bb\u7898\u82ef\u80fa\u884d\u751f\u7269\u4e2d\u7684N&#8211;\u53d6\u4ee3\u57fa\u4e3a-Ts\u3001-Boc\u4ee5\u53ca-Ac\u65f6\uff0c\u5747\u80fd\u591f\u987a\u5229\u5730\u53c2\u4e0e\u4e0a\u8ff0\u7684\u73af\u5316\u8fc7\u7a0b\uff0c\u5e76\u83b7\u5f97\u76f8\u5e94\u7684\u73af\u5316\u4ea7\u726919a&#8211;19c\u3002\u540c\u65f6\uff0c\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\uff0c\u5bf9\u4e8e\u90bb\u7898\u82ef\u80fa\u5e95\u7269\u82ef\u57fa\u4e2d\u5b58\u5728\u7684\u4e00\u7cfb\u5217\u7535\u5b50\u4e0e\u7acb\u4f53\u6548\u5e94\u4e0d\u540c\u7684\u53d6\u4ee3\u57fa\u56e2\uff0c\u5747\u80fd\u591f\u826f\u597d\u5730\u517c\u5bb9\uff0c\u5e76\u83b7\u5f97\u76f8\u5e94\u7684\u56db\u6c22\u5494\u5511\u4ea7\u726922&#8211;30\u3002\u540c\u65f6\uff0c\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u8868\u73b0\u51fa\u4f18\u826f\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u3002\u4e4b\u540e\uff0c\u8be5\u5c0f\u7ec4\u8fdb\u4e00\u6b65\u5bf9\u5404\u7c7b\u6742\u73af\u5e95\u7269\u4ee5\u53ca\u6742\u73af\u8054\u70ef\u524d\u4f53\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76\u3002\u5b9e\u9a8c\u8868\u660e\uff0c\u5177\u6709\u6eb4\u5421\u5576\u57fa\u4ee5\u53ca\u7898\u5421\u5576\u57fa\u7684\u6742\u73af\u5e95\u7269\u540c\u6837\u80fd\u591f\u7ecf\u5386\u9884\u671f\u7684\u73af\u5316\u8fc7\u7a0b\uff0c\u5e76\u4ee5\u826f\u597d\u81f3\u4f18\u826f\u7684\u53cd\u5e94\u6536\u7387\u83b7\u5f97\u76f8\u5e94\u76ee\u6807\u4ea7\u726931\u3002\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u4f5c\u4e3a\u73af\u8054\u70ef\u524d\u4f53\u7684\u7845\u57fa\u4e09\u6c1f\u7532\u78fa\u9178\u916f13\u7684\u76f8\u5e94\u6c27\u6742\u4e0e\u6c2e\u6742\u884d\u751f\u7269\uff0c\u5747\u80fd\u591f\u8f83\u597d\u5730\u4e0e\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u4f53\u7cfb\u517c\u5bb9\uff0c\u5e76\u83b7\u5f97\u76f8\u5e94\u7684\u76ee\u6807\u4ea7\u726932&#8211;33\u3002\u5e76\u4e14\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u89c2\u5bdf\u5230\uff0c\u4e03\u5143\u73af\u8054\u70ef\u524d\u4f53\u540c\u6837\u80fd\u591f\u987a\u5229\u5730\u53c2\u4e0e\u4e0a\u8ff0\u7684\u73af\u5316\u8fc7\u7a0b\uff0c\u5e76\u83b7\u5f97\u76f8\u5e94\u7684\u6742\u73af\u4ea7\u726934\u3002 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D. Roberts, H. E. Simmons, L. A. Carlsmith, C. W.\u00a0Vaughan,\u00a0J. Am. Chem. Soc. 1953, 75, 3290.\u00a0doi:\u00a010.1021\/ja01109a523. [2]\u00a0G. 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