{"id":41908,"date":"2022-05-31T08:00:58","date_gmt":"2022-05-31T00:00:58","guid":{"rendered":"\/\/www.gsbet888.com\/?p=41908"},"modified":"2022-05-30T21:43:50","modified_gmt":"2022-05-30T13:43:50","slug":"angew%ef%bc%9a%e8%9e%ba%e7%bc%a9%e9%85%ae%e4%b8%8e%e8%9e%ba%e7%bc%a9%e9%86%9b%e8%83%ba%e7%9a%84%e5%af%b9%e6%98%a0%e9%80%89%e6%8b%a9%e6%80%a7%e5%90%88%e6%88%90%e6%96%b9%e6%b3%95%e5%ad%a6%e7%a0%94","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2022\/05\/angew%ef%bc%9a%e8%9e%ba%e7%bc%a9%e9%85%ae%e4%b8%8e%e8%9e%ba%e7%bc%a9%e9%86%9b%e8%83%ba%e7%9a%84%e5%af%b9%e6%98%a0%e9%80%89%e6%8b%a9%e6%80%a7%e5%90%88%e6%88%90%e6%96%b9%e6%b3%95%e5%ad%a6%e7%a0%94.html","title":{"rendered":"Angew\uff1a\u87ba\u7f29\u916e\u4e0e\u87ba\u7f29\u919b\u80fa\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5408\u6210\u65b9\u6cd5\u5b66\u7814\u7a76"},"content":{"rendered":"<p>\u672c\u6587\u4f5c\u8005:\u6749\u6749<\/p>\n<h4 style=\"font-weight: 400;\">\u5bfc\u8bfb\uff1a<\/h4>\n<p style=\"font-weight: 400;\">\u8fd1\u65e5\uff0c\u534e\u4e1c\u7406\u5de5\u5927\u5b66\u7684\u9093\u536b\u5e73\u4e0e\u6768\u6b66\u6797\u8bfe\u9898\u7ec4\u5728<em>Angew. Chem. Int. Ed.<\/em>\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u901a\u8fc7\u91d1\u4e0e\u94f1\u4e32\u8054\u50ac\u5316\u7684\u5916\u6d88\u65cb2-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u915a\u4e0e\u7094\u9187\/\u7094\u9170\u80fa\u4e4b\u95f4\u7684\u5bf9\u6620\u9009\u62e9\u6027\u70ef\u4e19\u57fa\u5316\/\u87ba\u7f29\u916e\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u6210\u529f\u5b8c\u6210\u4e00\u7cfb\u5217\u624b\u6027\u87ba\u7f29\u916e\u4ee5\u53ca\u87ba\u7f29\u919b\u80fa (spiroaminals)\u5206\u5b50\u7684\u6784\u5efa\u3002\u540c\u65f6\uff0c\u8be5\u5c0f\u7ec4\u8fdb\u4e00\u6b65\u53d1\u73b0\uff0c\u91c7\u7528\u5916\u6d88\u65cb2-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u82ef\u80fa\u4f5c\u4e3a\u53cd\u5e94\u5e95\u7269\u65f6\uff0c\u5219\u80fd\u591f\u901a\u8fc7\u76f8\u5173\u7684KR\u8fc7\u7a0b\uff0c\u8fdb\u800c\u5206\u522b\u83b7\u5f97\u5404\u7c7b\u5bf9\u6620\u5bcc\u96c6\u7684\u87ba\u7f29\u919b\u80fa\u4ee5\u53ca\u76f8\u5e94\u7684\u624b\u60272-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u82ef\u80fa\u8d77\u59cb\u539f\u6599\u3002<\/p>\n<blockquote>\n<p style=\"font-weight: 400;\">Enantioselective Synthesis of Spiroketals and Spiroaminals via Gold and Iridium Sequential Catalysis<\/p>\n<p>Yang, X. Shang, X. Luo, W. Deng, <em>Angew. Chem. Int. Ed<\/em>. <strong>2022<\/strong>, ASAP. doi: <a href=\"https:\/\/doi.org\/10.1002\/anie.202203661\">10.1002\/anie.202203661<\/a>.<\/p><\/blockquote>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/2-14.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41898 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/2-14.png\" alt=\"\" width=\"675\" height=\"164\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/2-14.png 675w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/2-14-300x73.png 300w\" sizes=\"(max-width: 675px) 100vw, 675px\" \/><\/a><\/p>\n<h4 style=\"font-weight: 400;\">\u6b63\u6587\uff1a<\/h4>\n<p style=\"font-weight: 400;\">\u87ba\u7f29\u916e\u7ed3\u6784\u5355\u5143\u5e7f\u6cdb\u5b58\u5728\u4e8e\u4e00\u7cfb\u5217\u751f\u7269\u6d3b\u6027\u5929\u7136\u4ea7\u7269\u4ee5\u53ca\u5404\u7c7b\u836f\u7406\u6d3b\u6027\u5206\u5b50\u4e2d (Figure 1)\u3002\u540c\u65f6\uff0c\u87ba\u7f29\u916e\u9aa8\u67b6\u540c\u6837\u5b58\u5728\u4e8e\u5404\u7c7b\u91cd\u8981\u7684\u624b\u6027\u914d\u4f53\u4e2d<sup>[1]<\/sup>\u3002\u800c\u4e14\uff0c\u5728\u8fc7\u53bb\u7684\u51e0\u5341\u5e74\u91cc\uff0c\u5df2\u7ecf\u6210\u529f\u8bbe\u8ba1\u51fa\u591a\u79cd\u7528\u4e8e\u6784\u5efa\u5bf9\u6620\u5bcc\u96c6\u7684\u87ba\u7f29\u916e\u5206\u5b50\u7684\u5408\u6210\u8f6c\u5316\u7b56\u7565<sup>[2]-[3]<\/sup>\u3002\u5c24\u5176\u91c7\u7528\u73af\u5916\u4e59\u70ef\u57fa\u919a (exocyclic vinyl ethers)\u6216\u70ef\u9170\u80fa\u4e0e\u5404\u7c7b\u4e24\u4eb2\u6027\u5e95\u7269\u8fdb\u884c\u7684\u4e32\u8054\u52a0\u6210\/\u87ba\u7f29\u916e\u53cd\u5e94\u65b9\u6cd5\u5b66\u7684\u76f8\u5173\u7814\u7a76\uff0c\u5df2\u7ecf\u5907\u53d7\u8bf8\u591a\u7814\u7a76\u56e2\u961f\u7684\u5e7f\u6cdb\u5173\u6ce8<sup>[4]-[6] <\/sup>(Scheme 1a)\u3002\u7136\u800c\uff0c\u5bf9\u4e8e\u9009\u62e9\u5176\u4ed6\u4e24\u4eb2\u6027\u780c\u5757\u8fdb\u4e00\u6b65\u6784\u5efa\u7ed3\u6784\u66f4\u4e3a\u591a\u6837\u5316\u7684\u87ba\u7f29\u916e\u5206\u5b50\uff0c\u5219\u4ecd\u6709\u5f85\u8fdb\u4e00\u6b65\u7814\u7a76\u3002\u8fd9\u91cc\uff0c\u53d7\u5230\u672c\u8bfe\u9898\u7ec4\u524d\u671f\u5bf9\u4e8e\u5c06\u65b0\u578b<em>\u03c0<\/em>-ally-Ir\u4e24\u4eb2\u6027\u914d\u5408\u7269\u5e94\u7528\u4e8e\u6784\u5efa\u5bf9\u6620\u5bcc\u96c6\u7684benzo[<em>b<\/em>]oxocines\u5206\u5b50<sup>[7]<\/sup>\u76f8\u5173\u7814\u7a76\u62a5\u9053\u7684\u542f\u53d1\uff0c\u534e\u4e1c\u7406\u5de5\u5927\u5b66\u7684\u9093\u536b\u5e73\u4e0e\u6768\u6b66\u6797\u56e2\u961f\u6210\u529f\u8bbe\u8ba1\u51fa\u4e00\u79cd\u5168\u65b0\u7684\u901a\u8fc7Au\/Ir-\u50ac\u5316\u5242\u4fc3\u8fdb\u76842-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u82ef\u915a\u4e0e\u7094\u9187\/\u7094\u9170\u80fa\u4e4b\u95f4\u7684\u73af\u5f02\u6784\u5316\/\u70ef\u4e19\u57fa\u5316\/\u87ba\u7f29\u916e\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u987a\u5229\u5b8c\u6210\u4e00\u7cfb\u5217\u624b\u6027\u87ba\u7f29\u916e\u4e0e\u87ba\u7f29\u919b\u80fa\u5206\u5b50\u7684\u6784\u5efa(Scheme 1b)\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/3-12.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41899 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/3-12-680x481.png\" alt=\"\" width=\"680\" height=\"481\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/3-12-680x481.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/3-12-300x212.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/3-12.png 729w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/a><\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/4-10.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41900 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/4-10-680x607.png\" alt=\"\" width=\"680\" height=\"607\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/4-10-680x607.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/4-10-300x268.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/4-10.png 720w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/a><\/p>\n<p style=\"font-weight: 400;\">\u9996\u5148\uff0c\u4f5c\u8005\u91c7\u75282-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u82ef\u915a(\u00b1)-<strong>1a<\/strong>\u4e0e\u7094\u9170\u80fa<strong>2a<\/strong>\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u76f8\u5173\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\u7528[Ir(cod)Cl]<sub>2<\/sub>\u4e0eAuPPh<sub>3<\/sub>Cl\u4f5c\u4e3a\u50ac\u5316\u5242\uff0c(<em>S<\/em>)-<strong>L1 <\/strong>(Carreira <em>P<\/em>-olefin ligand)\u4f5c\u4e3a\u624b\u6027\u914d\u4f53\uff0cMgSO<sub>4<\/sub>\u4f5c\u4e3a\u6dfb\u52a0\u5242\uff0cFe(OTf)<sub>2<\/sub>\u4f5c\u4e3a\u9178\u4fc3\u8fdb\u5242 (acid promoter)\uff0cCH<sub>2<\/sub>Cl<sub>2<\/sub>\u4f5c\u4e3a\u53cd\u5e94\u6eb6\u5242\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a\u5ba4\u6e29\uff0c\u6700\u7ec8\u83b7\u5f9778%\u6536\u7387\u7684\u624b\u6027\u4ea7\u7269<strong>3a <\/strong>(&gt;20:1<em> dr<\/em>, 99% ee)\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/5-7.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41901 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/5-7-593x1024.png\" alt=\"\" width=\"593\" height=\"1024\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/5-7-593x1024.png 593w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/5-7-174x300.png 174w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/5-7.png 758w\" sizes=\"(max-width: 593px) 100vw, 593px\" \/><\/a><\/p>\n<p style=\"font-weight: 400;\">\u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u5bf9\u4e00\u7cfb\u52172-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u915a (Scheme 2 )\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/6.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41902 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/6-680x563.jpg\" alt=\"\" width=\"680\" height=\"563\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/6-680x563.jpg 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/6-300x249.jpg 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/6.jpg 700w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/a><\/p>\n<p style=\"font-weight: 400;\">\u4e4b\u540e\uff0c\u8be5\u5c0f\u7ec4\u5c06\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u4f53\u7cfb\u8fdb\u4e00\u6b65\u5e94\u7528\u4e8e\u4e00\u7cfb\u5217\u87ba\u7f29\u916e\u5206\u5b50\u7684\u6784\u5efa (Scheme 3)\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/7-2.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41903 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/7-2-680x752.png\" alt=\"\" width=\"680\" height=\"752\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/7-2-680x752.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/7-2-271x300.png 271w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/7-2.png 725w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/a><\/p>\n<p style=\"font-weight: 400;\">\u540c\u65f6\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u5bf9\u4e8e\u4e00\u7cfb\u5217\u4e0d\u540c\u57fa\u56e2\u53d6\u4ee3\u76842-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u82ef\u80fa\u5e95\u7269 (\u00b1)-<strong>6<\/strong>\u540c\u6837\u80fd\u591f\u6709\u6548\u5730\u517c\u5bb9\uff0c\u5e76\u4ee5\u4e2d\u7b49\u7a0b\u5ea6\u7684\u53cd\u5e94\u6536\u7387\u4ee5\u53ca\u4ee5\u53ca\u4f18\u826f\u7684\u5bf9\u6620\u9009\u62e9\u6027\uff0c\u83b7\u5f97\u9884\u671f\u7684\u87ba\u7f29\u919b\u80fa\u4ea7\u7269 (Scheme 4)\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/8-2.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41904 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/8-2-680x318.png\" alt=\"\" width=\"680\" height=\"318\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/8-2-680x318.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/8-2-300x140.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/8-2-768x359.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/8-2.png 922w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/a><\/p>\n<p style=\"font-weight: 400;\">\u4e4b\u540e\uff0c\u8be5\u5c0f\u7ec4\u901a\u8fc7\u5982\u4e0b\u7684\u4e00\u7cfb\u5217\u7814\u7a76\u8fdb\u4e00\u6b65\u8868\u660e\uff0c\u8fd9\u4e00\u5168\u65b0\u7684\u4e32\u8054\u53cd\u5e94\u7b56\u7565\u5177\u6709\u6f5c\u5728\u7684\u5408\u6210\u5e94\u7528\u4ef7\u503c(Scheme 5)\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/9-3.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41905 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/9-3-641x1024.png\" alt=\"\" width=\"641\" height=\"1024\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/9-3-641x1024.png 641w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/9-3-188x300.png 188w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/9-3-768x1227.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/9-3.png 772w\" sizes=\"(max-width: 641px) 100vw, 641px\" \/><\/a><\/p>\n<p style=\"font-weight: 400;\">\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u901a\u8fc7\u4e00\u7cfb\u5217\u76f8\u5173\u7684\u63a7\u5236\u5b9e\u9a8c (Scheme 6)\u7814\u7a76\u8868\u660e\uff0c\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u53ef\u80fd\u6d89\u53caAu\u50ac\u5316\u7684\u73af\u5f02\u6784\u5316(cycloisomerization)\u4ee5\u53caIr\u50ac\u5316\u7684\u5206\u6b65\u70ef\u4e19\u57fa\u5316\/\u87ba\u7f29\u916e\u5316\u7684\u4e32\u8054\u53cd\u5e94\u8def\u5f84\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/10-3.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41906 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/10-3-680x227.png\" alt=\"\" width=\"680\" height=\"227\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/10-3-680x227.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/10-3-300x100.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/10-3.png 729w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/a><\/p>\n<p style=\"font-weight: 400;\">\u57fa\u4e8e\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u7814\u7a76\u4ee5\u53ca\u524d\u671f\u76f8\u5173\u7684\u6587\u732e\u62a5\u9053<sup>[8]-[9]<\/sup>\uff0c\u4f5c\u8005\u63d0\u51fa\u5982\u4e0b\u5408\u7406\u7684\u53cd\u5e94\u673a\u7406\u4ee5\u53ca\u76f8\u5173\u7684\u5bf9\u6620\u9009\u62e9\u6027\u63a7\u5236\u6a21\u578b (Scheme 7)\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/11-3.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41907 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/11-3-680x349.png\" alt=\"\" width=\"680\" height=\"349\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/11-3-680x349.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/11-3-300x154.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/11-3-768x395.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/05\/11-3.png 874w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/a><\/p>\n<h4 style=\"font-weight: 400;\">\u603b\u7ed3\uff1a<\/h4>\n<p style=\"font-weight: 400;\">\u534e\u4e1c\u7406\u5de5\u5927\u5b66\u7684\u9093\u536b\u5e73\u4e0e\u6768\u6b66\u6797\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u901a\u8fc7\u91d1\u4e0e\u94f1\u4e32\u8054\u50ac\u5316\u7684\u5916\u6d88\u65cb2-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u82ef\u915a\u4e0e\u7094\u9187\/\u7094\u9170\u80fa\u4e4b\u95f4\u7684\u5bf9\u6620\u9009\u62e9\u6027\u70ef\u4e19\u57fa\u5316\/\u87ba\u7f29\u916e\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u6210\u529f\u5b8c\u6210\u4e00\u7cfb\u5217\u624b\u6027\u87ba\u7f29\u916e\u4e0e\u87ba\u7f29\u919b\u80fa (spiroaminals)\u5206\u5b50\u7684\u6784\u5efa\u3002\u540c\u65f6\uff0c\u8be5\u5c0f\u7ec4\u8fdb\u4e00\u6b65\u53d1\u73b0\uff0c\u91c7\u7528\u5916\u6d88\u65cb2-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u82ef\u80fa\u4f5c\u4e3a\u53cd\u5e94\u5e95\u7269\u65f6\uff0c\u5219\u80fd\u591f\u901a\u8fc7\u76f8\u5173\u7684KR\u8fc7\u7a0b\uff0c\u5206\u522b\u83b7\u5f97\u5bf9\u6620\u4f53\u5bcc\u96c6\u7684\u87ba\u7f29\u919b\u80fa\u4ee5\u53ca\u76f8\u5e94\u7684\u624b\u60272-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u82ef\u80fa\u5e95\u7269\u3002\u8fd9\u4e00\u5168\u65b0\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5408\u6210\u8f6c\u5316\u7b56\u7565\u5177\u6709\u9ad8\u5ea6\u7684\u975e\u5bf9\u6620\u9009\u62e9\u6027\u4e0e\u4f18\u826f\u7684\u5bf9\u6620\u9009\u62e9\u6027\u4ee5\u53ca\u826f\u597d\u7684\u5408\u6210\u5e94\u7528\u4ef7\u503c\u7b49\u4f18\u52bf\u3002<\/p>\n<h4 style=\"font-weight: 400;\"><strong>\u53c2\u8003\u6587\u732e\uff1a<\/strong><\/h4>\n<ul>\n<li style=\"font-weight: 400;\">[1] (a) X. Wang, Z. Han, Z. Wang, K. Ding, <em>Acc. Chem. Res. <\/em><strong>2021<\/strong>, <em>54<\/em>, 668. doi: <a href=\"https:\/\/doi.org\/10.1021\/acs.accounts.0c00697\">10.1021\/acs.accounts.0c00697<\/a>.<\/li>\n<li style=\"font-weight: 400;\">(b) J. Huang, M. Hong, C. Wang, S. Kramer, G. Lin, X. Sun, <em>J. Org.<\/em> <em>Chem. <\/em><strong>2018<\/strong>, <em>83<\/em>, 12838. doi:<a href=\"https:\/\/doi.org\/10.1021\/acs.joc.8b01693\">10.1021\/acs.joc.8b01693<\/a>.<\/li>\n<li style=\"font-weight: 400;\">[2] (a) M. Wilsdorf, H. U. Reissig, <em>Angew. Chem. Int. Ed. <\/em><strong>2012<\/strong>, <em>51<\/em>, 9486. doi: <a href=\"https:\/\/doi.org\/10.1002\/anie.201203847\">10.1002\/anie.201203847<\/a>.<\/li>\n<li style=\"font-weight: 400;\">(b) R. Quach, D. F. Chorley, M. A. Brimble, <em>Org. Biomol. Chem. <\/em><strong>2014<\/strong>, <em>12<\/em>, 7423. doi: <a href=\"https:\/\/doi.org\/10.1039\/C4OB01325E\">10.1039\/C4OB01325E<\/a>.<\/li>\n<li style=\"font-weight: 400;\">(c) R. Quach, D. P. Furkert, M. A. Brimble, <em>Org. Biomol. Chem. <\/em><strong>2017<\/strong>, <em>15<\/em>, 3098. doi: <a href=\"https:\/\/doi.org\/10.1039\/C7OB00496F\">10.1039\/C7OB00496F<\/a>.<\/li>\n<li style=\"font-weight: 400;\">[3] (a) N. Liu, W. Zhu, J. Yao, L. Yin, T. Lu; X. Dou, <em>ACS Catal. <\/em><strong>2020<\/strong>, <em>10<\/em>, 2596. doi: <a href=\"https:\/\/doi.org\/10.1021\/acscatal.9b05577\">10.1021\/acscatal.9b05577<\/a>.<\/li>\n<li style=\"font-weight: 400;\">(b) L. Zhou, W. Yan, X. Sun, L. Wang, Y. Tang, <em>Angew. Chem. Int. Ed. <\/em><strong>2020<\/strong>, <em>59<\/em>, 18964. doi: <a href=\"https:\/\/doi.org\/10.1002\/anie.202007068\">10.1002\/anie.202007068<\/a>.<\/li>\n<li style=\"font-weight: 400;\">[4] S. Yu, L. Gao, Y. Yan, Z. Yin, Y. Shang, <em>Chin. J. Org. Chem. <\/em><strong>2021<\/strong>, <em>41<\/em>, 582. doi: <a href=\"https:\/\/doi.org\/10.6023\/cjoc202006050\">10.6023\/cjoc202006050<\/a>.<\/li>\n<li style=\"font-weight: 400;\">[5] (a) W. Mao, S. Lin, L. Zhang, H. Lu, J. Jia, Z. Xu, <em>Org. Chem. Front. <\/em><strong>2020<\/strong>, <em>7<\/em>, 856. doi: <a href=\"https:\/\/doi.org\/10.1039\/D0QO00022A\">10.1039\/D0QO00022A<\/a>.<\/li>\n<li style=\"font-weight: 400;\">(b) H. Wang, T. Zeng, X. Li, S. Wang, W. Xiao, L. Liu, W. Chang, J. Li, <em>Org. Chem. Front. <\/em><strong>2020<\/strong>, <em>7<\/em>, 1809. doi:<a href=\"https:\/\/doi.org\/10.1039\/D0QO00464B\">10.1039\/D0QO00464B<\/a>.<\/li>\n<li style=\"font-weight: 400;\">(c) T. Zeng, J. Kong, H. Wang, L. Liu, W. Chang, J. Li, <em>Adv. Synth. Catal. <\/em><strong>2021<\/strong>,<em> 363<\/em>, 4024. doi: <a href=\"https:\/\/doi.org\/10.1002\/adsc.202100523\">10.1002\/adsc.202100523<\/a>.<\/li>\n<li style=\"font-weight: 400;\">[6] (a) H. Wu, Y. He, L. Gong, <em>Org. Lett. <\/em><strong>2013<\/strong>, <em>15<\/em>, 460. doi: <a href=\"https:\/\/doi.org\/10.1021\/ol303188u\">10.1021\/ol303188u<\/a>.<\/li>\n<li style=\"font-weight: 400;\">(b) L. Cala, A. Mendoza, F. J. Fa\u00f1an\u00e1s, F. Rodr\u00edguez, <em>Chem. Commun. <\/em><strong>2013<\/strong>, <em>49<\/em>, 2715. doi: <a href=\"https:\/\/doi.org\/10.1039\/C3CC00118K\">10.1039\/C3CC00118K<\/a>.<\/li>\n<li style=\"font-weight: 400;\">(c) J. Li, L. Lin, B. Hu, X. Lian, G. Wang, X. Liu, X. Feng, <em>Angew. Chem. Int. Ed. <\/em><strong>2016<\/strong>, <em>55<\/em>, 6075. doi:<a href=\"https:\/\/doi.org\/10.1002\/anie.201601701\">10.1002\/anie.201601701<\/a>.<\/li>\n<li style=\"font-weight: 400;\">[7] W. Yang, Y. Wang, W. Li, B. Gu, S. Wang, X. Luo, B. Tian, W. Deng, <em>ACS Catal. <\/em><strong>2021<\/strong>, <em>11<\/em>, 12557. doi:<a href=\"https:\/\/doi.org\/10.1021\/acscatal.1c03711\">10.1021\/acscatal.1c03711<\/a>.<\/li>\n<li style=\"font-weight: 400;\">[8] D. Li, K. Shi, X. Mao, Z. Zhao, X. Wu, P. Liu, <em>Tetrahedron <\/em><strong>2014<\/strong>, <em>70<\/em>, 7022. doi: <a href=\"https:\/\/doi.org\/10.1016\/j.tet.2014.06.078\">10.1016\/j.tet.2014.06.078<\/a>.<\/li>\n<li style=\"font-weight: 400;\">[9] (a) S. L. Ro\u0308ssler, S. Krautwald, E. M. Carreira, <em>J. Am. Chem. Soc. <\/em><strong>2017<\/strong>, <em>139<\/em>, 3603. doi: <a href=\"https:\/\/doi.org\/10.1021\/jacs.6b12421\">10.1021\/jacs.6b12421<\/a>.<\/li>\n<li style=\"font-weight: 400;\">(b) B. Bhaskararao, R. B. Sunoj, <em>J. Am. Chem. Soc.<\/em> <strong>2015<\/strong>, <em>137<\/em>, 15712. doi: <a href=\"https:\/\/doi.org\/10.1021\/jacs.5b05902\">10.1021\/jacs.5b05902<\/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","protected":false},"excerpt":{"rendered":"\u672c\u6587\u4f5c\u8005:\u6749\u6749 \u5bfc\u8bfb\uff1a \u8fd1\u65e5\uff0c\u534e\u4e1c\u7406\u5de5\u5927\u5b66\u7684\u9093\u536b\u5e73\u4e0e\u6768\u6b66\u6797\u8bfe\u9898\u7ec4\u5728Angew. Chem. Int. Ed.\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u901a\u8fc7\u91d1\u4e0e\u94f1\u4e32\u8054\u50ac\u5316\u7684\u5916\u6d88\u65cb2-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u915a\u4e0e\u7094\u9187\/\u7094\u9170\u80fa\u4e4b\u95f4\u7684\u5bf9\u6620\u9009\u62e9\u6027\u70ef\u4e19\u57fa\u5316\/\u87ba\u7f29\u916e\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u6210\u529f\u5b8c\u6210\u4e00\u7cfb\u5217\u624b\u6027\u87ba\u7f29\u916e\u4ee5\u53ca\u87ba\u7f29\u919b\u80fa (spiroaminals)\u5206\u5b50\u7684\u6784\u5efa\u3002\u540c\u65f6\uff0c\u8be5\u5c0f\u7ec4\u8fdb\u4e00\u6b65\u53d1\u73b0\uff0c\u91c7\u7528\u5916\u6d88\u65cb2-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u82ef\u80fa\u4f5c\u4e3a\u53cd\u5e94\u5e95\u7269\u65f6\uff0c\u5219\u80fd\u591f\u901a\u8fc7\u76f8\u5173\u7684KR\u8fc7\u7a0b\uff0c\u8fdb\u800c\u5206\u522b\u83b7\u5f97\u5404\u7c7b\u5bf9\u6620\u5bcc\u96c6\u7684\u87ba\u7f29\u919b\u80fa\u4ee5\u53ca\u76f8\u5e94\u7684\u624b\u60272-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u82ef\u80fa\u8d77\u59cb\u539f\u6599\u3002 Enantioselective Synthesis of Spiroketals and Spiroaminals via Gold and Iridium Sequential Catalysis Yang, X. Shang, X. Luo, W. Deng, Angew. Chem. Int. Ed. 2022, ASAP. doi: 10.1002\/anie.202203661. \u6b63\u6587\uff1a \u87ba\u7f29\u916e\u7ed3\u6784\u5355\u5143\u5e7f\u6cdb\u5b58\u5728\u4e8e\u4e00\u7cfb\u5217\u751f\u7269\u6d3b\u6027\u5929\u7136\u4ea7\u7269\u4ee5\u53ca\u5404\u7c7b\u836f\u7406\u6d3b\u6027\u5206\u5b50\u4e2d (Figure 1)\u3002\u540c\u65f6\uff0c\u87ba\u7f29\u916e\u9aa8\u67b6\u540c\u6837\u5b58\u5728\u4e8e\u5404\u7c7b\u91cd\u8981\u7684\u624b\u6027\u914d\u4f53\u4e2d[1]\u3002\u800c\u4e14\uff0c\u5728\u8fc7\u53bb\u7684\u51e0\u5341\u5e74\u91cc\uff0c\u5df2\u7ecf\u6210\u529f\u8bbe\u8ba1\u51fa\u591a\u79cd\u7528\u4e8e\u6784\u5efa\u5bf9\u6620\u5bcc\u96c6\u7684\u87ba\u7f29\u916e\u5206\u5b50\u7684\u5408\u6210\u8f6c\u5316\u7b56\u7565[2]-[3]\u3002\u5c24\u5176\u91c7\u7528\u73af\u5916\u4e59\u70ef\u57fa\u919a (exocyclic vinyl ethers)\u6216\u70ef\u9170\u80fa\u4e0e\u5404\u7c7b\u4e24\u4eb2\u6027\u5e95\u7269\u8fdb\u884c\u7684\u4e32\u8054\u52a0\u6210\/\u87ba\u7f29\u916e\u53cd\u5e94\u65b9\u6cd5\u5b66\u7684\u76f8\u5173\u7814\u7a76\uff0c\u5df2\u7ecf\u5907\u53d7\u8bf8\u591a\u7814\u7a76\u56e2\u961f\u7684\u5e7f\u6cdb\u5173\u6ce8[4]-[6] (Scheme 1a)\u3002\u7136\u800c\uff0c\u5bf9\u4e8e\u9009\u62e9\u5176\u4ed6\u4e24\u4eb2\u6027\u780c\u5757\u8fdb\u4e00\u6b65\u6784\u5efa\u7ed3\u6784\u66f4\u4e3a\u591a\u6837\u5316\u7684\u87ba\u7f29\u916e\u5206\u5b50\uff0c\u5219\u4ecd\u6709\u5f85\u8fdb\u4e00\u6b65\u7814\u7a76\u3002\u8fd9\u91cc\uff0c\u53d7\u5230\u672c\u8bfe\u9898\u7ec4\u524d\u671f\u5bf9\u4e8e\u5c06\u65b0\u578b\u03c0-ally-Ir\u4e24\u4eb2\u6027\u914d\u5408\u7269\u5e94\u7528\u4e8e\u6784\u5efa\u5bf9\u6620\u5bcc\u96c6\u7684benzo[b]oxocines\u5206\u5b50[7]\u76f8\u5173\u7814\u7a76\u62a5\u9053\u7684\u542f\u53d1\uff0c\u534e\u4e1c\u7406\u5de5\u5927\u5b66\u7684\u9093\u536b\u5e73\u4e0e\u6768\u6b66\u6797\u56e2\u961f\u6210\u529f\u8bbe\u8ba1\u51fa\u4e00\u79cd\u5168\u65b0\u7684\u901a\u8fc7Au\/Ir-\u50ac\u5316\u5242\u4fc3\u8fdb\u76842-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u82ef\u915a\u4e0e\u7094\u9187\/\u7094\u9170\u80fa\u4e4b\u95f4\u7684\u73af\u5f02\u6784\u5316\/\u70ef\u4e19\u57fa\u5316\/\u87ba\u7f29\u916e\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u987a\u5229\u5b8c\u6210\u4e00\u7cfb\u5217\u624b\u6027\u87ba\u7f29\u916e\u4e0e\u87ba\u7f29\u919b\u80fa\u5206\u5b50\u7684\u6784\u5efa(Scheme 1b)\u3002 \u9996\u5148\uff0c\u4f5c\u8005\u91c7\u75282-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u82ef\u915a(\u00b1)-1a\u4e0e\u7094\u9170\u80fa2a\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u76f8\u5173\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\u7528[Ir(cod)Cl]2\u4e0eAuPPh3Cl\u4f5c\u4e3a\u50ac\u5316\u5242\uff0c(S)-L1 (Carreira P-olefin ligand)\u4f5c\u4e3a\u624b\u6027\u914d\u4f53\uff0cMgSO4\u4f5c\u4e3a\u6dfb\u52a0\u5242\uff0cFe(OTf)2\u4f5c\u4e3a\u9178\u4fc3\u8fdb\u5242 (acid promoter)\uff0cCH2Cl2\u4f5c\u4e3a\u53cd\u5e94\u6eb6\u5242\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a\u5ba4\u6e29\uff0c\u6700\u7ec8\u83b7\u5f9778%\u6536\u7387\u7684\u624b\u6027\u4ea7\u72693a (&gt;20:1 dr, 99% ee)\u3002 \u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u5bf9\u4e00\u7cfb\u52172-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u915a (Scheme 2 )\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76\u3002 \u4e4b\u540e\uff0c\u8be5\u5c0f\u7ec4\u5c06\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u4f53\u7cfb\u8fdb\u4e00\u6b65\u5e94\u7528\u4e8e\u4e00\u7cfb\u5217\u87ba\u7f29\u916e\u5206\u5b50\u7684\u6784\u5efa (Scheme 3)\u3002 \u540c\u65f6\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u5bf9\u4e8e\u4e00\u7cfb\u5217\u4e0d\u540c\u57fa\u56e2\u53d6\u4ee3\u76842-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u82ef\u80fa\u5e95\u7269 (\u00b1)-6\u540c\u6837\u80fd\u591f\u6709\u6548\u5730\u517c\u5bb9\uff0c\u5e76\u4ee5\u4e2d\u7b49\u7a0b\u5ea6\u7684\u53cd\u5e94\u6536\u7387\u4ee5\u53ca\u4ee5\u53ca\u4f18\u826f\u7684\u5bf9\u6620\u9009\u62e9\u6027\uff0c\u83b7\u5f97\u9884\u671f\u7684\u87ba\u7f29\u919b\u80fa\u4ea7\u7269 (Scheme 4)\u3002 \u4e4b\u540e\uff0c\u8be5\u5c0f\u7ec4\u901a\u8fc7\u5982\u4e0b\u7684\u4e00\u7cfb\u5217\u7814\u7a76\u8fdb\u4e00\u6b65\u8868\u660e\uff0c\u8fd9\u4e00\u5168\u65b0\u7684\u4e32\u8054\u53cd\u5e94\u7b56\u7565\u5177\u6709\u6f5c\u5728\u7684\u5408\u6210\u5e94\u7528\u4ef7\u503c(Scheme 5)\u3002 \u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u901a\u8fc7\u4e00\u7cfb\u5217\u76f8\u5173\u7684\u63a7\u5236\u5b9e\u9a8c (Scheme 6)\u7814\u7a76\u8868\u660e\uff0c\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u53ef\u80fd\u6d89\u53caAu\u50ac\u5316\u7684\u73af\u5f02\u6784\u5316(cycloisomerization)\u4ee5\u53caIr\u50ac\u5316\u7684\u5206\u6b65\u70ef\u4e19\u57fa\u5316\/\u87ba\u7f29\u916e\u5316\u7684\u4e32\u8054\u53cd\u5e94\u8def\u5f84\u3002 \u57fa\u4e8e\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u7814\u7a76\u4ee5\u53ca\u524d\u671f\u76f8\u5173\u7684\u6587\u732e\u62a5\u9053[8]-[9]\uff0c\u4f5c\u8005\u63d0\u51fa\u5982\u4e0b\u5408\u7406\u7684\u53cd\u5e94\u673a\u7406\u4ee5\u53ca\u76f8\u5173\u7684\u5bf9\u6620\u9009\u62e9\u6027\u63a7\u5236\u6a21\u578b (Scheme 7)\u3002 \u603b\u7ed3\uff1a \u534e\u4e1c\u7406\u5de5\u5927\u5b66\u7684\u9093\u536b\u5e73\u4e0e\u6768\u6b66\u6797\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u901a\u8fc7\u91d1\u4e0e\u94f1\u4e32\u8054\u50ac\u5316\u7684\u5916\u6d88\u65cb2-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u82ef\u915a\u4e0e\u7094\u9187\/\u7094\u9170\u80fa\u4e4b\u95f4\u7684\u5bf9\u6620\u9009\u62e9\u6027\u70ef\u4e19\u57fa\u5316\/\u87ba\u7f29\u916e\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u6210\u529f\u5b8c\u6210\u4e00\u7cfb\u5217\u624b\u6027\u87ba\u7f29\u916e\u4e0e\u87ba\u7f29\u919b\u80fa (spiroaminals)\u5206\u5b50\u7684\u6784\u5efa\u3002\u540c\u65f6\uff0c\u8be5\u5c0f\u7ec4\u8fdb\u4e00\u6b65\u53d1\u73b0\uff0c\u91c7\u7528\u5916\u6d88\u65cb2-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u82ef\u80fa\u4f5c\u4e3a\u53cd\u5e94\u5e95\u7269\u65f6\uff0c\u5219\u80fd\u591f\u901a\u8fc7\u76f8\u5173\u7684KR\u8fc7\u7a0b\uff0c\u5206\u522b\u83b7\u5f97\u5bf9\u6620\u4f53\u5bcc\u96c6\u7684\u87ba\u7f29\u919b\u80fa\u4ee5\u53ca\u76f8\u5e94\u7684\u624b\u60272-(1-\u7f9f\u57fa\u70ef\u4e19\u57fa)\u82ef\u80fa\u5e95\u7269\u3002\u8fd9\u4e00\u5168\u65b0\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5408\u6210\u8f6c\u5316\u7b56\u7565\u5177\u6709\u9ad8\u5ea6\u7684\u975e\u5bf9\u6620\u9009\u62e9\u6027\u4e0e\u4f18\u826f\u7684\u5bf9\u6620\u9009\u62e9\u6027\u4ee5\u53ca\u826f\u597d\u7684\u5408\u6210\u5e94\u7528\u4ef7\u503c\u7b49\u4f18\u52bf\u3002 \u53c2\u8003\u6587\u732e\uff1a [1] (a) X. Wang, Z. Han, Z. Wang, K. Ding, Acc. Chem. Res. 2021, 54, 668. doi: 10.1021\/acs.accounts.0c00697. (b) J. Huang, M. Hong, C. Wang, S. Kramer, G. Lin, X. 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