{"id":4143,"date":"2024-08-02T10:07:52","date_gmt":"2024-08-02T02:07:52","guid":{"rendered":"\/\/www.30-onna.com\/?p=4143"},"modified":"2024-08-02T10:07:52","modified_gmt":"2024-08-02T02:07:52","slug":"crabtree%e5%af%bc%e5%90%91%e6%b0%a2%e5%8c%96%e5%82%ac%e5%8c%96%e5%89%82","status":"publish","type":"post","link":"\/\/www.30-onna.com\/archives\/4143","title":{"rendered":"Crabtree\u5bfc\u5411\u6c22\u5316\u50ac\u5316\u5242"},"content":{"rendered":"

Crabtree\u5bfc\u5411\u6c22\u5316\u50ac\u5316\u5242<\/strong><\/a>\u200b<\/p>\n

\u5bfc\u5411\u6027\u70ef\u70c3\u6c22\u5316\u50ac\u5316\u5242\u2014\u2014\u94f1\u50ac\u5316\u5242\uff1a[Ir(cod)(PCy3)pyr]PF6\u6216\u4e0a\u56fe\u7684\u50ac\u5316\u52423 {BArF=\u56db[2,5-\u4e8c(\u4e09\u6c1f\u7532\u6c27\u57fa)\u82ef\u57fa]\u787c}\u3002\u5e38\u89c1\u7684\u5bfc\u5411\u57fa\u56e2\uff1aOH, OMe, C55O, CO2Me, C(O)NR2\u3002\u6b64\u50ac\u5316\u5242\u7531Crabtree RH\u65e9\u57281979\u5e74\u53d1\u73b0\u3002<\/p>\n

\"Crabtree\u5bfc\u5411\u6c22\u5316\u50ac\u5316\u5242\u63d2\u56fe\"<\/p>\n

Roskamp-Feng\u53cd\u5e94<\/p>\n

1989\u5e74\uff0cRoskamp\u9996\u5148\u62a5\u9053\u4e86\u5229\u7528\u6c2f\u5316\u4e9a\u9521\u50ac\u5316\u4e59\u57fa\u91cd\u6c2e\u4e59\u9178\u4e59\u916f\u548c\u919b\u53cd\u5e94\u5236\u5907\u03b2-\u916e\u916f\u7684\u53cd\u5e94\u3010J. Org. Chem., 1989, 54, 3258\u3011\u3002\u7ecf\u8fc7\u4e8c\u5341\u591a\u5e74\u7684\u53d1\u5c55\u5404\u79cd\u8def\u6613\u65af\u9178\uff08Sc(OTf)3\uff0cBF3, GeCl2\uff09\u90fd\u53ef\u7528\u4e8e\u6b64\u53cd\u5e94\u30022011\u5e74\uff0c\u56db\u5ddd\u5927\u5b66\u5316\u5b66\u5b66\u9662\u51af\u5c0f\u660e\u6559\u6388\uff0c\u4ee5\u624b\u6027\u6c2e\u6c27\u2013Sc(OTf)3\u7edc\u5408\u7269\u50ac\u5316\u5242\u5b9e\u73b0\u4e86\u9996\u4f8b\u50ac\u5316\u4e0d\u5bf9\u79f0Roskamp\u53cd\u5e94\u3002<\/p>\n

Reformatsky\u53cd\u5e94<\/p>\n

\u7531\u03b1-\u5364\u4ee3\u916f\u548c\u950c\u7c89\u5236\u5907\u5f97\u5230\u7684\u6709\u673a\u950c\u8bd5\u5242\u5bf9\u7fb0\u57fa\u5316\u5408\u7269\uff08\u919b\u3001\u916e\u3001\u916f\uff09\u8fdb\u884c\u4eb2\u6838\u52a0\u6210\u751f\u6210\u03b2-\u7f9f\u57fa\u916f\u7684\u53cd\u5e94\u3002<\/p>\n

\u4e0d\u540c\u7684\u03b1-\u5364\u4ee3\u916f\u7684\u6d3b\u6027\u6b21\u5e8f\u4e3a\uff1a\u7898\u4ee3\u9178\u916f\uff1e\u6eb4\u4ee3\u9178\u916f\uff1e\u6c2f\u4ee3\u9178\u916f\uff1e\u6c1f\u4ee3\u9178\u916f\uff0c\u56e0\u6c1f\u548c\u6c2f\u4ee3\u916f\u4e0d\u6d3b\u6cfc\uff0c\u800c\u7898\u4ee3\u916f\u8f83\u96be\u5236\u5907\uff0c\u6545\u5e38\u7528\u6eb4\u4ee3\u9178\u916f\u3002\u53cd\u5e94\u6eb6\u5242\u5e38\u7528\u7edd\u5bf9\u65e0\u6c34\u6709\u673a\u6eb6\u5242\uff0c\u5e38\u7528\u7684\u6709\u4e59\u919a\u3001\u82ef\u3001\u7532\u82ef\u3001\u4e8c\u7532\u82ef\u7b49\u3002<\/p>\n

\"Crabtree\u5bfc\u5411\u6c22\u5316\u50ac\u5316\u5242\u63d2\u56fe1\"<\/p>\n

\u03b1-\u5364\u4ee3\u916f\u4e0d\u80fd\u4e0e\u9541\u53cd\u5e94\u751f\u6210\u683c\u6c0f\u8bd5\u5242\uff0c\u4f46\u6613\u4e0e\u950c\u5f62\u6210\u6709\u673a\u950c\u5316\u5408\u7269\u3002\u8fd9\u662f\u5236\u5907\u03b2-\u7f9f\u57fa\u916f\u7684\u4e00\u4e2a\u5f88\u597d\u7684\u65b9\u6cd5\u3002\u03b2-\u7f9f\u57fa\u916f\u53ef\u4ee5\u7528\u4e8e\u5236\u5907\u03b2-\u7f9f\u57fa\u9178\u548c\u03b1\uff0c\u03b2-\u4e0d\u9971\u548c\u916f\u3002<\/p>\n

\u6709\u673a\u950c\u8bd5\u5242\u7684\u6d3b\u6027\u6bd4\u683c\u6c0f\u8bd5\u5242\u4f4e\uff0c\u56e0\u6b64\u6b64\u53cd\u5e94\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u9ad8\uff0c\u4f46\u53cd\u5e94\u8f83\u6162\u3002\u8fd1\u5e74\u6765\uff0c\u4e5f\u6709\u53d1\u73b0\u9664\u950c\u4ee5\u5916\u7684\u91d1\u5c5e\u4e5f\u80fd\u53d1\u751f\u7c7b\u4f3c\u7684\u53cd\u5e94\uff0c\u7279\u522b\u662fSm(II)\u3001Cr(II)\u3001Ti(II)\uff0cB\uff08III\uff09\u7b49\u3002<\/p>\n

Luche\u950c\u70ef\u4e19\u5316\u53cd\u5e94<\/p>\n

Hill-Barrett\u9499\u50ac\u5316\u7684\u6c22\u80fa\u5316\u53cd\u5e94<\/p>\n

Fujiwara\u9567\u7cfb\u91d1\u5c5e\u50ac\u5316\u53cd\u5e94<\/p>\n

\u82b3\u9999\u916e\u6216\u82b3\u9999\u5364\u4ee3\u7269\u4e0e\u9567\u7cfb\u91d1\u5c5e\uff08\u5982\u9571\uff0cYb\uff09\u7edc\u5408\u540e\uff0c\u5bf9\u916e\uff0c\u8148\uff0c\u73af\u6c27\u5316\u7269\u548c\u5364\u4ee3\u7269\u7b49\u8fdb\u884c\u4eb2\u6838\u52a0\u6210\u6216\u4eb2\u6838\u53d6\u4ee3\u7684\u53cd\u5e94\u3002<\/p>\n

\"Crabtree\u5bfc\u5411\u6c22\u5316\u50ac\u5316\u5242\u63d2\u56fe2\"<\/p>\n

\u91d1\u5c5e\u50ac\u5316\u7684\u8ba1\u91cf\u785d\u5316\u53cd\u5e94<\/p>\n

Grignard\u53cd\u5e94\uff08\u683c\u6c0f\u53cd\u5e94\uff09<\/p>\n

Kabachnik-Fields\u53cd\u5e94<\/p>\n

1952\u5e74\uff0c M. I. Kabachinik\u7b49\u4eba\u62a5\u9053\u4e86\u4e09\u7ec4\u5206\u5408\u6210\u03b1-\u80fa\u57fa\u81a6\u9178\u7684\u53cd\u5e94\u3002\u9178\u50ac\u5316\u4e0b\uff0c\u4f2f\u80fa\u6216\u4ef2\u80fa\uff0c\u919b\u916e\u548c\u4e9a\u81a6\u9178\u4e8c\u70f7\u57fa\u916f\u8fdb\u884c\u4e09\u7ec4\u5206\u53cd\u5e94\u5f97\u5230\u03b1-\u80fa\u57fa\u81a6\u9178\u3002\u5e95\u7269\u9664\u4e86\u4e9a\u81a6\u9178\u4e8c\u70f7\u57fa\u916f\uff0c\u4e9a\u81a6\u9178\u548c\u81a6\u9178\u4e09\u70f7\u57fa\u916f\u4e5f\u80fd\u8fdb\u884c\u6b64\u53cd\u5e94\u3002\u5e38\u89c1\u7684\u50ac\u5316\u5242\u6709\uff0c\u4e09\u6c1f\u7532\u78fa\u9178\u7684\u9567\u7cfb\u91d1\u5c5e\u76d0(Sc, Yb, Sm, In)\u6216Al, Co, Ni\u7684\u915e\u83c1\u7edc\u5408\u7269\u3002<\/p>\n

\u5173\u73af\u590d\u5206\u89e3\u53cd\u5e94\u3010Ring-closing metathesis (RCM)\u3011<\/p>\n

\u662f\u6307\u5728\u91d1\u5c5e\u50ac\u5316\u4e0b\u7684\u78b3\u78b3\u53cc\u952e\u7684\u5207\u65ad\u5e76\u91cd\u65b0\u7ed3\u5408\u8fdb\u884c\u5173\u73af\u7684\u53cd\u5e94\u3002\u662f\u70ef\u70c3\u590d\u5206\u89e3\u53cd\u5e94\u4e2d\u7684\u4e00\u79cd\u3002<\/p>\n

\u70ef\u70c3\u4ea4\u53c9\u590d\u5206\u89e3\u53cd\u5e94<\/p>\n

\u70ef\u70c3\u4ea4\u53c9\u590d\u5206\u89e3\u53cd\u5e94\u662f\u6307\u4e24\u79cd\u7aef\u57fa\u70ef\u70c3\u5728Ru(II)-\u5361\u5bbe(Grubbs Catalyst)\u50ac\u5316\u4e0b\uff0c\u653e\u51fa\u4e59\u70ef\u7684\u70ef\u70c3\u590d\u5206\u89e3\u53cd\u5e94\u3002\u4ece\u7edf\u8ba1\u5b66\u6765\u770b\uff0c\u53cd\u5e94\u5e94\u8be5\u751f\u6210\u4e09\u79cd\u53ef\u80fd\u7684\u51e0\u4f55\u5f02\u6784\u4f53\uff0c\u518d\u52a0\u4e0a\u6bcf\u79cd\u5f02\u6784\u4f53\u5404\u6709 E\/Z\u6784\u578b\uff0c\u56e0\u6b64\u5171\u6709\u516d\u79cd\u4ea7\u7269\u3002<\/p>\n","protected":false},"excerpt":{"rendered":"

Crabtree\u5bfc\u5411\u6c22\u5316\u50ac\u5316\u5242\u200b \u5bfc\u5411\u6027\u70ef\u70c3\u6c22\u5316\u50ac\u5316\u5242\u2014\u2014\u94f1\u50ac\u5316\u5242\uff1a[Ir(cod)(PCy3)pyr]PF6\u6216\u4e0a\u56fe\u7684\u50ac\u5316\u52423 {BArF=\u56db[2,5-\u4e8c(\u4e09\u6c1f\u7532\u6c27\u57fa)\u82ef\u57fa]\u787c}\u3002\u5e38\u89c1\u7684\u5bfc\u5411\u57fa\u56e2\uff1aOH… <\/p>\n","protected":false},"author":2,"featured_media":4144,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"footnotes":""},"categories":[45],"tags":[],"_links":{"self":[{"href":"\/\/www.30-onna.com\/wp-json\/wp\/v2\/posts\/4143"}],"collection":[{"href":"\/\/www.30-onna.com\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"\/\/www.30-onna.com\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"\/\/www.30-onna.com\/wp-json\/wp\/v2\/users\/2"}],"replies":[{"embeddable":true,"href":"\/\/www.30-onna.com\/wp-json\/wp\/v2\/comments?post=4143"}],"version-history":[{"count":1,"href":"\/\/www.30-onna.com\/wp-json\/wp\/v2\/posts\/4143\/revisions"}],"predecessor-version":[{"id":4147,"href":"\/\/www.30-onna.com\/wp-json\/wp\/v2\/posts\/4143\/revisions\/4147"}],"wp:featuredmedia":[{"embeddable":true,"href":"\/\/www.30-onna.com\/wp-json\/wp\/v2\/media\/4144"}],"wp:attachment":[{"href":"\/\/www.30-onna.com\/wp-json\/wp\/v2\/media?parent=4143"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"\/\/www.30-onna.com\/wp-json\/wp\/v2\/categories?post=4143"},{"taxonomy":"post_tag","embeddable":true,"href":"\/\/www.30-onna.com\/wp-json\/wp\/v2\/tags?post=4143"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}