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鍙戝睍鏂板弽搴旀潵瀹炵幇鏈夋満鍒嗗瓙涓箍娉涘瓨鍦ㄧ殑鍏厓鐜殑楂樻晥鍚堟垚锛屼竴鐩翠互鏉ラ兘鏄湁鏈哄寲瀛︾爺绌剁殑閲嶈璇鹃涔嬩竴銆傚叾涓紝鏈�涓鸿憲鍚嶄笖甯哥敤鐨勫弽搴旀槸Diels-Alder鍙嶅簲锛岃繖涓�鍙嶅簲涔熻幏寰椾簡1950骞?/span>璇鸿礉灏斿寲瀛﹀銆備絾涓嶅悓鍒嗗瓙鐨勫彇浠ｅ崈宸竾鍒紝绔嬩綋鍖栧涔熶笉涓�鏍凤紝鏈夋満鍖栧瀹朵滑浠嶇劧闇�瑕佸彂灞曟柊鐨勫弽搴旀潵楂樻晥鍚堟垚涓嶅悓鐨勫叚鍏冪幆缁撴瀯銆?/span>
浣欏織绁?/span>璇鹃缁勭殑鐮旂┒鏂瑰悜涔嬩竴灏辨槸鍙戝睍鏂板瀷鎴愮幆鍙嶅簲锛屼负鍖栧瀹跺悎鎴愬悇绉嶅垎瀛愭彁渚涘悎鎴愬伐鍏枫�備粬浠棰樼粍鍙戝睍浜嗙敤浜庡叚鍏冪⒊鐜悎鎴愮殑[5+1]銆?/span> [5+1]/[2+2+1]鍜?/span>[3+2+1]鍙嶅簲銆傚叾涓殑[3+2+1]鍙嶅簲閲囩敤閾戜綔涓哄偓鍖栧墏锛屼箼鐑熀鐜笝鐑蜂綔涓轰笁纰崇粍鍒嗭紝鐑儍鎴栫倲鐑冧綔涓轰簩纰崇粍鍒嗭紝涓�姘у寲纰充綔涓轰竴纰崇粍鍒嗭紝鍙互鐢ㄦ潵鍚堟垚涓嶅悓鍙栦唬鐨勫叚鍏冪⒊鐜�傝繖涓�鍙嶅簲宸茬粡鍦?/span>galanthamine锛?/span>J. Org. Chem. 2015, 80, 1952锛夈�?/span>gracilamine锛?/span>J. Org. Chem. 2016, 81, 6757锛夈�?/span>伪-agarofuran锛?/span>Org. Lett. 2010, 12, 2528锛夈�?/span>clovan-2,9-dione锛?/span>Org. Lett. 2017, 19, 6040 & Org. Lett. 2022, 24, 5902锛夈�?/span>ent-kaurane diterpenoids锛?/span>J. Am. Chem. Soc. 2020, 142, 2238锛?/span>鍖栧闄?/span>闆锋檽鍏夎棰樼粍鎴愭灉锛夌瓑澶氱澶╃劧浜х墿鍜岃嵂鐗╂椿鎬у垎瀛愮殑鍚堟垚涓緱鍒板簲鐢紙鍥?/span>1锛夈�?/span>[3+2+1]鍙嶅簲涓�涓緝涓洪仐鎲剧殑鍦版柟鏄鍙嶅簲鑷充粖杩樻病鏈夊彂灞曞嚭鍏朵笉瀵圭О鍌寲鐗堟湰锛屼竴鑸彧鑳介�氳繃搴曠墿鐨勬墜鎬у熀鍥㈣繘琛岃瀵兼潵瀹炵幇鍏夊娲绘�х幆鍔犳垚浜х墿鐨勫悎鎴愩�?/span>
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鏈�杩戯紝浣欏織绁ヨ棰樼粍鍙戝睍浜嗚[3+2+1]鐨勪竴涓叏鏂扮殑鐗堟湰锛屽嵆閾戝偓鍖栫殑[4+2]鍙嶅簲锛堝浘2锛?/span> J. Am. Chem. Soc. 2022, 144, 21457鈥?/span>21469锛夈�備粬浠?/span>閲囩敤涔欑儻鍩虹幆涓侀叜锛堝彲浠ヨ涓烘槸涔欑儻鍩虹幆涓欑兎鍜屼竴姘у寲纰崇殑绛変环鐗╋級浣滀负鍥涚⒊缁勫垎锛岀倲鐑冧綔涓轰袱纰崇粍鍒嗭紝鐢变竴浠烽搼涓庤矾鏄撴柉閰稿崗鍚屽偓鍖栨潵鏋勭瓚5/6骞剁幆鎴?/span>6/6骞剁幆浣撶郴銆?/span>璇?/span>[4+2]鍙嶅簲鏄�氳繃鍦ㄧ幆涓侀叜2-浣嶅紩鍏ヤ箼鐑熀鍙栦唬浣滀负瀵煎悜鍩鸿瀵奸搼瀵圭幆涓侀叜鐨勭⒊-纰抽敭娲诲寲锛屽悓鏃堕叜缇板熀鍙互涓庤矾鏄撴柉閰搁厤浣嶏紝杩涗竴姝ユ椿鍖栫幆涓侀叜鐨勭⒊-纰抽敭銆傝繖涓�鍗忓悓鍌寲妯″紡閫夋嫨鎬у垏鏂景鍩轰笌瀛ｇ⒊涓績涔嬮棿鐨勭⒊-纰抽敭锛屼笉浠呮垚鍔熷湴鏋勫缓鍏厓鐜郴锛岃繕鎴愬姛鎷撳睍鍒扮兎鍩哄強澶氱鐢靛瓙鏁堝簲鐨勮姵鍩轰笂锛屽ぇ閮ㄥ垎搴曠墿閮藉叿鏈変腑绛夊埌鑹ソ鐨勬敹鐜囷紝瀵规鞍鍩猴紝閰景鍩猴紝閰熀鍙婇叞鑳虹瓑瀹樿兘鍥㈠叿鏈夎壇濂界殑鍏煎鎬с�?/span>[4+2]鍙嶅簲鍙互浣跨敤鎵嬫�х殑鐜竵閰紝骞跺湪鍙嶅簲涓皢搴曠墿鐨勬墜鎬т紶閫掑埌鏈�缁堜骇鐗╋紝浠庤�屾瀯寤哄叿鏈夋ˉ澶存墜鎬у纰充腑蹇冪殑鍙岀幆浜х墿銆傝[4+2]鍙嶅簲涓殑涔欑儻鍩轰篃鍙互杩涜澶氬彇浠ｏ紝杩欏ぇ澶ф嫇灞曚簡鍙嶅簲鐨勫簲鐢ㄨ寖鍥淬�?/span>
鍥?. 浣欏織绁ヨ棰樼粍鍙戝睍鐨刐4+2]鍙嶅簲鍙婂簳鐗╅�傜敤鑼冨洿锛堝浘鐗囨潵鑷?span style="margin: 0px; padding: 0px; -webkit-font-smoothing: subpixel-antialiased; font-style: italic;">JACS锛?/span>
鍩轰簬瑙嗚鍔ㄥ姏瀛﹀垎鏋愬拰DFT璁＄畻锛堝叿浣撶粏鑺傝鍙傝�冩枃绔狅級锛屼綔鑰呮彁鍑轰簡鍥?/span>3鎵�绀虹殑鏈虹悊銆傚偓鍖栨椿鎬х墿绉?/span>A鐢卞弽搴斿惊鐜箣澶栫殑浜岃仛浣撲紤鐪犳�佽В绂荤敓鎴愩�傜劧鍚庯紝閫氳繃TS-OA鍙戠敓姘у寲鍔犳垚杩囩▼锛岃繖涓�姝ヨ璁や负鏄弽搴旂殑鍐抽�熸锛岄殢鍚庡簳鐗╀腑鐨勭倲閰嶄綅鍚庣敓鎴?/span>B銆傜粡杩囬厤浣嶇倲鐨勮縼绉绘彃鍏ャ�佽繕鍘熸秷闄ゅ拰鍌寲鍓傝浆绉伙紝鏈�缁堝舰鎴愮幆鍔犳垚浜х墿2銆傚叾涓?/span>ZnCl2锛堟垨ZnI2锛夎璁や负鍏锋湁淇冭繘C鈭扖鐨勬椿鍖栧拰鍘熶綅鐢熸垚娲绘�ч槼绂诲瓙閾戠殑浣滅敤銆?/span>
鍥?. 鍩轰簬鍔ㄥ姏瀛︾爺绌跺拰DFT璁＄畻鎵�鎻愮殑鍙嶅簲鏈虹悊锛堝浘鐗囨潵鑷?span style="margin: 0px; padding: 0px; -webkit-font-smoothing: subpixel-antialiased; font-style: italic;">JACS锛?/span>
璇ョ爺绌跺伐浣滄槸鍦ㄤ綑蹇楃ゥ鏁欐巿鎸囧涓嬬敱璇鹃缁勭殑鍗氬＋鐮旂┒鐢熷紶绠″畤銆佸紶鏀�鍙婃潕鍐版枃浣滀负鍏卞悓绗竴浣滆�呭畬鎴愮殑锛屽垬搴峰崥澹拰鏉庝繆鍗氬＋鍦ㄨ鐮旂┒鐨勫墠鏈熸帰绱腑鍋氬嚭浜嗛噸瑕佽础鐚�傛劅璋㈠浗瀹惰嚜鐒剁瀛﹀熀閲戝銆佸寳浜垎瀛愮瀛﹀浗瀹剁爺绌朵腑蹇冪殑璧勫姪鍜屽寳浜ぇ瀛﹂珮鎬ц兘璁＄畻骞冲彴鐨勬敮鎸併�?/span>
Dual Activation Strategy to AchieveC鈭扖 Cleavage of Cyclobutanes: Development andMechanism of Rh and Zn Co-catalyzed [4 + 2] Cycloaddition ofYne-Vinylcyclobutanones.
Guan-Yu Zhang, Pan Zhang, Bing-Wen Li, Kang Liu, Jun Li, and Zhi-Xiang Yu J. Am. Chem. Soc. 2022, 144, 21457鈥?/span>21469.