瀹為獙瀹ゆ柊闂?/h4>
浣欏織绁ヨ棰樼粍鍗佷簲骞寸殑[5+2+1]鍙嶅簲鏈虹悊鐮旂┒鍙栧緱杩涘睍
浣欏織绁ヨ棰樼粍鐨勭爺绌舵柟鍚?/span>涔嬩竴鏄彂灞曟柊鐨?/span>鎴愮幆鍙嶅簲锛?/span>骞跺皢鍏跺簲鐢ㄥ埌澶╃劧浜х墿銆?/span>鑽墿浠ュ強鍏?/span>浠?/span>鍔熻兘鍒嗗瓙鐨?/span>鍚堟垚涓?/span>銆?/span>鍚屾椂锛?/span>璇鹃缁?/span>涔?/span>閫氳繃璁＄畻鍖栧鍜?/span>鏈虹悊瀹為獙鐮旂┒鍙嶅簲鏈虹悊銆?/span>浣欏織绁ヨ棰樼粍鑷垚绔嬩互鏉?/span>锛?/span>宸?/span>鍙戝睍浜?/span>涓�绯诲垪鎴愮幆鍙嶅簲锛屽彲鐢ㄤ簬鍚堟垚娑电洊浠庡洓鍏冪幆鍒板叓鍏冪幆鐨勭幆绯?/span>缁撴瀯銆?/span>杩欎簺鍙嶅簲涓湁澶氫釜鍙嶅簲琚?/span>浣欏織绁ヨ棰樼粍鍜屽浗鍐呭澶氫釜璇鹃缁勭敤浜庡ぉ鐒朵骇鐗╃殑鍏ㄥ悎鎴愩�?/span>鍏朵腑锛?/font>鐢ㄤ簬鍏厓鐜悎鎴愮殑閾?/span>鍌寲鐨勭儻-涔欑儻鍩虹幆涓欑兎锛?/span>ene-VCP锛変笌涓�姘у寲纰?/span>鐨?/span>[5+2+1]鐜姞鎴?/span>鍙嶅簲鐢?/span>浣欏織绁ヨ棰樼粍鍦?/span>2007骞?/span>棣栨鎶ラ亾(鍥?/span>1)銆傝鍙嶅簲涓哄寲瀛﹀鍚堟垚鏋佸叿鎸戞垬鎬?/span>鐨勫叓鍏?/span>纰?/span>鐜彁渚?/span>浜?/span>闈炲父楂樻晥鐨勬柟娉?/span>锛屽凡琚?/span>澶氭搴旂敤浜?/span>鍏锋湁鍏厓纰崇幆楠ㄦ灦鐨勫ぉ鐒朵骇鐗╁強涓夊鐑风被澶╃劧浜х墿锛堝熀浜?/span>5/8骞剁幆鐨勮法鐜弽搴旓級鐨勫叏鍚堟垚銆備緥濡傦紝浣欏織绁ヨ棰樼粍鏈�杩?/span>鎶ラ亾鐨?/span>鍒╃敤[5+2+1]鐜姞鎴?/span>鍙嶅簲鍏鍚堟垚澶╃劧浜х墿isohirsut-4-ene锛?/span>Org. Lett. 2022, 24, 1444鈭?447锛?/span>銆?/span>
鍥?/span>1锛?/span> [5+2+1]鍙嶅簲鍜屽埄鐢ㄨ鍙嶅簲宸?/span>鍚堟垚鐨?/span>澶╃劧浜х墿鍒嗗瓙锛堜汉鐗╃礌鎻忕敱娣卞湷甯?/span>榫欏崕鍖?/span>瀹為獙瀛︽牎鍒濅腑閮ㄥ鐢熸矆娆ｆ彁渚涳級
鐒惰�岋紝浣欏織绁ヨ棰樼粍鍦ㄧ爺绌惰鍙嶅簲鏈虹悊鐨?/span>杩囩▼涓?/span>鍗?/span>閬囧埌浜嗚澶?/span>鍥伴毦銆?/span>棣栧厛锛?/span>瀵逛簬鍍?/span>[5+2+1]鐜姞鎴?/span>鍙嶅簲杩欎竴绫昏繃娓￠噾灞炲偓鍖栫殑澶氭鍙嶅簲锛屽緢闅鹃�夋嫨鍚堥�傜殑璁＄畻鏂规硶鏉ュ噯纭弿杩版墍鏈?/span>鐨?/span>鍩哄厓姝ラ锛屽閰嶄綋鐨?/span>閰?/span>浣嶄笌瑙ｇ銆佹哀鍖栧姞鎴愩�?/span>杩佺Щ鎻掑叆鍜?/span>杩樺師娑堥櫎銆傛澶栵紝璇嗗埆鐪熸鐨?/span>鍌寲鐗╃骞朵簡瑙?/span>鍏?/span>鏄浣?/span>浜?/span>鐢熺殑涔熸槸涓�椤瑰洶闅剧殑浠诲姟銆?/span>鏈�杩戯紝浣欏織绁?/span>璇鹃缁?/span>鎶ラ亾浜?/span>[5+2+1]鐜姞鎴愬弽搴旂殑璇︾粏鏈虹悊鐮旂┒锛屽杩欎釜鍥版壈浠栦滑鍗佷簲骞寸殑鏈虹悊闂鏈変簡娣卞叆鐨勭悊瑙?/span>銆備綔鑰呴鍏?/span>鍊熷姪瑙嗚鍔ㄥ姏瀛﹀垎鏋愭帰绌?/span>浜?/span>鍙嶅簲浣撶郴涓湡姝ｇ殑鍌寲鐗╃銆備粬浠?/span>鍙戠幇[5+2+1]鐜姞鎴愬弽搴斿浜庡偓鍖栧墏[Rh(CO)2Cl]2鍜?/span>姘фˉ搴曠墿1a閮芥槸0.5绾х殑锛岃繖琛ㄦ槑鍙屾牳浼戠湢绉嶅拰鍗曟牳鍌寲鐗╃涔嬮棿瀛樺湪鍖栧骞宠 骞舵湁搴曠墿鍙備笌鍏朵腑(鍥?/span>2)銆傚熀浜庢锛岃棰樼粍鐮旂┒浜哄憳鎻愬嚭鍙嶅簲鐨勪紤鐪犵鍖呭惈涓や釜閾?/span>涓績鍙婁竴涓簳鐗╁垎瀛愶紝鑰屽偓鍖栫墿绉嶅寘鍚竴涓搼涓績鍜屼竴涓簳鐗╁垎瀛?/span>銆?/span>姝ゅ锛?/span>璇鹃缁勭爺绌舵垚鍛?/span>杩樺彂鐜?/span>CO鐨勭骇鏁?/span>鏄浂锛?/span>杩?/span>琛?/span>鏄?/span>浼戠湢绉嶄腑CO鐨?/span>涓暟鏄弽搴斿喅閫熸杩囨浮鎬佷腑CO涓暟鐨勪袱鍊嶏紙鍚庣画鐨?/span>璁＄畻鍖栧鐮旂┒琛ㄦ槑鍐抽�熸杩囨浮鎬佷腑鍙?/span>鍚?/span>鏈?/span>涓�涓?/span>CO閰嶄綋锛夈�?/span>瀵?/span>浜?/span>姘ˉ搴曠墿1b锛屼綑蹇楃ゥ璇鹃缁?/span>鍙戠幇鍌寲鍓?/span>鍜屽簳鐗╃殑绾ф暟浠嶇劧閮?/span>鏄?/span>0.5锛屼絾鏄?/span>瀵逛簬CO鐨勭骇鏁?/span>鏄?/span>-0.5锛岀爺绌惰�?/span>璁や负杩欐槸鐢变簬浼戠湢绉?/span>鐨勭粍鎴?/span>鍙戠敓浜?/span>鍙樺寲銆傚偓鍖栫墿绉嶅舰鎴愮殑杩囩▼涓渶瑕?/span>浠庝紤鐪犵涓?/span>瑙ｇ鍑?/span>CO锛岃繖浣垮緱CO鍒?/span>鍘嬪澶у弽鑰屼細瀵瑰弽搴斾骇鐢熶竴瀹氱殑鎶戝埗銆?/span>
鍥?/span>2. 鍙屾牳浼戠湢鐗╃涓庡崟鏍稿偓鍖栫墿绉嶄箣闂寸殑杞寲锛?/span>鍥剧墖鏉ユ簮锛?/span>JACS锛?/span>銆?/span>
鎺ヤ笅鏉ワ紝璇鹃缁勭爺绌?/span>鎴?/span>鍛?/span>鍒╃敤缁嗚嚧鐨?/span>璁＄畻鍖栧鏂规硶鍩哄噯鐮旂┒璇勪及浜嗕笉鍚岃绠楁柟娉曞湪棰勬祴閾?/span>鍌寲鐜姞鎴愬弽搴斿熀鍏冩楠ょ殑鐑姏瀛﹀拰鍔ㄥ姏瀛︿笂鐨勮〃鐜帮紝骞舵渶缁堝喅瀹氬垎鍒娇鐢?/span>BMK娉涘嚱鍜?/span>DLPNO-CCSD(T)鏂规硶杩涜缁撴瀯浼樺寲鍜岄珮绮惧害鍗曠偣鑳借绠椼�傜爺绌剁粨鏋?/span>琛ㄦ槑[5+2+1]鐜姞鎴愬弽搴?/span>鐨勫偓鍖栧惊鐜?/span>浠?/span>鍗曟牳閾?/span>鐗╃涓庡簳鐗?/span>鐨?/span>閰嶄綅鍑哄彂锛?/span>闅忓悗鍙戠敓姘у寲鍔犳垚銆?/span>鐑儍鎻?/span>鍏?/span>鍜岀景鍩?/span>鎻掑叆锛屾渶鍚?/span>閫氳繃杩樺師娑堥櫎寰楀埌鐩稿簲鐨?/span>5/8骞剁幆浜?/span>鐗?/span> (鍥?/span>3鍜屽浘4)銆?/span>璇?/span>[5+2+1]鍙嶅簲涓?/span>姘у寲鍔犳垚锛堝嵆鐜笝鐑风殑寮�鐜楠わ級鏄?/span>璇?/span>鍙嶅簲鐨勫喅閫熸锛?/span>鑰屽彲鑳界殑[5+2]鍙嶅簲涓殑杩樺師娑堥櫎姝ラ鍦ㄥ姩鍔涘涓婃瘮CO鐨勯厤浣?/span>/鎻掑叆鎱㈣�屼笉鑳戒笌[5+2+1]鍙嶅簲绔炰簤锛?/span>浠庤�?/span>寰堝ソ鍦?/span>鐞嗚В浜嗚鍙嶅簲鍙戠敓鐨勫師鍥?/span>銆?/span>
鍥?/span>3. [5+2+1]鐜姞鎴愬弽搴旂殑鍌寲寰幆锛?/span>鍥剧墖鏉ユ簮锛?/span>JACS锛?/span>銆?/span>
鍥?/span>4. [5+2+1]鐜姞鎴愬弽搴斿湪DLPNO-CCSD(T)/def2-TZVPP:SMD(1,4-dioxane)//BMK/def2-SVP姘村钩涓嬭绠?/span>寰楀埌鐨勫悏甯冩柉鑷敱鑳介潰 锛?/span>鍥剧墖鏉ユ簮锛?/span>JACS锛?/span>銆?/span>
闄ゆ浠ュ锛?/span>鐮旂┒鑰?/span>缁撳悎鏈虹悊瀹為獙鍜岃绠楀寲瀛﹀搴曠墿鐨?/span>鍙嶅簲娲?/span>鎬?/span>銆佸弽搴旂殑绔嬩綋閫夋嫨鎬у拰鍖栧閫夋嫨鎬ц繘琛屼簡璁ㄨ锛岀敱姝ゅ畬鎴愪簡瀵?/span>[5+2+1]鐜姞鎴愬弽搴旀満鐞嗙殑绯荤粺鎬х爺绌?/span>銆?/span>瀵硅宸ヤ綔鍗佷簲骞寸殑鐮旂┒缁撴灉鐨勨�滀竴浜斾竴鍗佲�濈殑璇︾粏鎻忚堪鍙互鍙傝�冨師鏂囩尞 (Yi Wang, Wei Liao, Yuanyuan Wang, Lei Jiao, and Zhi-Xiang Yu, J. Am. Chem. Soc. 2022, 144, 2624-2636锛夈�?/span>
[5+2+1]鐜姞鎴?/span>鍙嶅簲鐨?/span>鏈虹悊鐮旂┒鏄湪浣欏織绁?/span>鏁欐巿鎸囧涓嬬敱璇鹃缁勭殑鐜嬬啝鍗氬＋銆?/span>寤栦紵鍗氬＋锛岀帇婧愭簮鍗氬＋銆佺劍闆峰崥澹?/span>瀹屾垚銆?/span>璇ラ」鐩緱鍒?/span>浜?/span>鍩洪噾濮旈噸鐐归」鐩?/span>銆婇噾灞炲偓鍖栫幆鍔犳垚鍙嶅簲鏈虹悊鐮旂┒鍜屽弽搴斿彂灞曘�嬶紙21933003锛夈�佸寳浜垎瀛愮瀛﹀浗瀹剁爺绌朵腑蹇?/span>鍜屽寳浜ぇ瀛﹂珮鎬ц兘璁＄畻骞冲彴鐨?/span>澶у姏鏀寔銆?/span>