瀹為獙瀹ゆ柊闂?/h4>
閽偓鍖栫殑鐜笝鐑椿鎬?鍙帶鐑熀鍔犳垚鑱氬悎鐮旂┒鏂拌繘灞?/h1>
浣滆�咃細
鏉ユ簮锛?nbsp;
鍙戝竷鏃ユ湡:2021-10-22
鐜笝鐑槸涓�绫绘渶灏忕殑涓嶉ケ鍜岀幆鐘跺寲鍚堢墿, 鐢变簬鍏锋湁寰?/span>楂?/span>鐨?/span>鐜?/span>寮犲姏锛?/span>寮犲姏鑳斤細鐜笝鐑?8 kcal/mol; 鐜笝鐑?4kcal/mol锛?/span>銆?/span>鍥犺�?/span>鍏锋湁涓板瘜鐨勫弽搴旀�э紝鍦ㄦ湁鏈哄寲瀛︿腑鏈夊崄鍒嗛噸瑕佺殑搴旂敤銆?/span>鍚屾椂锛屽叾鍦ㄩ珮鍒嗗瓙鑱氬悎鐮旂┒涓篃鏄竴绫?/span>鐙壒鐨勫崟浣?/span>銆?/span>灏界鐜笝鐑?/span>鍦ㄦ湁鏈哄悎鎴愬拰寮�鐜槗浣嶈仛鍚?/span>(ROMP)涓?/span>宸插睍鐜板嚭涓板瘜鍙嶅簲娲绘�?/span>锛屼絾鍏剁儻鍩?/span>鍔犳垚鑱氬悎鐨勭爺绌跺緢灏戯紝鑰岀浉搴旂殑娲绘�?鍙帶鑱氬悎浠嶇劧鏄竴涓?/span>灏氭湭瑙ｅ喅鐨勯棶棰?/span>銆?/span>鍏?/span>鎸戞垬鏉ヨ嚜浜庣幆涓欑儻娲绘�т腑闂翠綋鍐呭湪鐨勪笉绋冲畾鎬у拰閾惧闀?/span>杩囩▼涓?/span>鐨?/span>鍔ㄥ姏瀛?/span>闅滅绛?/span>銆?/span>
閽堝鍏锋湁楂?/span>搴?/span>鐜?/span>寮犲姏鐨?/span>鐜笝鐑?/span>鍗曚綋锛?/span>搴旂敤閲戝睘閰嶄綋鍜屽崟浣撳彇浠ｅ熀鍥㈢殑寮遍厤浣嶄綔鐢ㄥ崗鍚岃皟鑺傛椿鎬т腑蹇冪殑绋冲畾鎬т互鍙婇摼寮曞彂銆佸闀跨殑閫熺巼锛屾湁鍙兘瀹炵幇娲绘�?/span>/鍙帶鐨勮仛鍚堛�傚熀浜庤繖鏍风殑鎬濊矾锛?/span>鐜嬪墤娉?/span>鐮旂┒鍥㈤槦閫氳繃瀵逛笉鍚屽彇浠ｇ殑鐜笝鐑崟浣撶殑鐮旂┒锛屼娇鐢?/span>[Pd(allyl)Cl]2鍜?/span>澶т綅闃?/span>Wei-Phos閰嶄綋缁勬垚鐨勫偓鍖栦綋绯诲疄鐜颁簡3-鐢插熀-3-锛?/span>閰版哀鍩猴級鐢插熀鐜笝鐑?/span>鐨?/span>娲绘�?鍙帶鐑?/span>鍩?/span>鍔犳垚鑱氬悎銆?/span>
鍥?nbsp;1 Pd鍌寲鐨?/span>鐜笝鐑姞鎴愯仛鍚堝弽搴?/span>
浣滆�呬娇鐢?/span>3-鐢插熀-3-锛?/span>搴氶叞姘у熀锛?/span>鐢插熀鍙栦唬鐨勭幆涓欑儻鍗曚綋鐮旂┒浜嗕笉鍚岀殑纾烽厤浣撳鑱氬悎鍙嶅簲鐨勫奖鍝嶏紝褰撲娇鐢?/span>[Pd(allyl)Cl]2鍜?/span>Wei-Phos閰嶄綋缁勬垚鐨勫偓鍖栦綋绯?/span>鏃讹紝鑱氬悎鍙嶅簲闈?/span>甯稿揩閫燂紝鍙嶅簲鍙互鍦?/span>11鍒嗛挓鍐呭疄鐜板崟浣撶殑瀹屽叏杞寲銆?/span>鑱氬悎鐗?/span>鏁板潎鍒嗗瓙閲忎笌鍗曚綋/鍌寲鍓?/span>姣斾箣闂村憟鐜拌壇濂界殑绾挎�у叧绯汇�傚綋鍗曚綋/鍌寲鍓?/span>鐨勬瘮渚嬩负1000锛?鏃讹紝鎵�寰楄仛鍚堢墿鐨勬暟鍧囧垎瀛愰噺杈惧埌10.3涓?/span>锛堜富閾句笂澶х害525涓幆涓欑兎鐩存帴鐩歌繛锛?/span>銆?/span>瀹為獙琛ㄦ槑鑱氬悎杩囩▼涓崟浣撹浆鍖栫巼鍜屽垎瀛愰噺涔嬮棿鍛堢嚎鎬у叧绯伙紝涓斿垎瀛愰噺鍒嗗竷淇濇寔鍦ㄨ緝绐勭殑鏁板�艰寖鍥村唴銆傝繘涓�姝?/span>鍔ㄥ姏瀛?/span>瀹為獙琛ㄦ槑鑱氬悎鍙嶅簲鍜岀幆涓欑儻鍗曚綋涔嬮棿鍛堜竴绾у姩鍔涘锛岃仛鍚堝弽搴?/span>鍏锋湁蹇紩鍙戝拰鎱?/span>澧為暱鐨?/span>鐗瑰緛銆?/span>閫氳繃鍒跺缁撴瀯涓嶅悓鐨勫祵娈佃仛鍚?/span>鐗?/span>浣滆�?/span>杩涗竴姝ヨ瘉瀹炰簡璇ヨ仛鍚堢殑娲绘�у強鍙帶鎬?/span>銆?/span>
鍥?nbsp;2 鐜笝鐑彲鎺?/span>鍔犳垚鑱氬悎鐨勫姩鍔涘鐮旂┒
闅忓悗锛?/span>浣滆�?/span>鐮旂┒浜嗙幆涓欑儻鍗曚綋缁撴瀯瀵?/span>鑱氬悎鍙嶅簲鐨勫奖鍝?/span>锛屽彂鐜?/span>3-鐢插熀-3-锛?/span>閰版哀鍩?/span>锛?/span>鐢插熀鐜笝鐑?/span>鍗曚綋鐨勭敳鍩哄彇浠ｅ熀涓?/span>锛?/span>閰版哀鍩猴級鐢插熀涓婄殑缇板熀姘у師瀛愬浜庡弽搴旂殑鍙帶鎬ф槸鑷冲叧閲嶈鐨勶紱鍚屾椂浣滆�呬篃瀵逛笉鍚?/span>閽?/span>鍌寲鍓傜殑鍓嶄綋杩涜浜嗙爺绌讹紝褰撳皢[Pd(allyl)Cl]2涓殑-Cl鎹㈠仛-OAc鎴栬�呭姞鍏ュ叡鍌寲鍓?/span>AgOTf銆?/span>NaBPh4浠ュ強AgSbF4鏃讹紝閮戒細浣垮緱鑱氬悎鍙帶鎬т笅闄嶏紝鑰?/span>灏?/span>[Pd(allyl)Cl]2涓殑鐑笝鍩?/span>閰嶄綋鎹㈡垚鍏朵粬涓嶅悓鍙栦唬鐨?/span>鐑笝鍩?/span>閰嶄綋鏃跺垯瀵硅仛鍚堝弽搴旀病鏈夊奖鍝嶏紝鍥犳浣滆�呮帹娴嬪湪鑱氬悎寮曞彂鏃讹紝鍌寲鍓備腑鐨?/span>鐑笝鍩?/span>閰嶄綋浼樺厛鍙戠敓浜嗚縼绉绘彃鍏ヨ�?/span>-Cl鍒欎繚鎸佷笌閽?/span>涓?/span>蹇冪浉杩炪�傛澶栵紝浣滆�呬篃閫氳繃鏍哥姘㈣氨瀵?/span>鑱氬悎鐗╃殑绔熀缁?/span>鏋勮繘琛屽垎鏋?/span>锛?/span>杩涗竴姝ラ獙璇佷簡鐑笝鍩?/span>鑳藉浣滀负杩佺Щ鍩哄洟鏉ュ紩鍙戣仛鍚堣繃绋嬨�?/span>浣滆�呭涓嶅悓鐩镐技楠ㄦ灦鐨勯厤浣撲篃杩涜浜嗙爺绌讹紝鍙戠幇Wei-Phos閰嶄綋楠ㄦ灦涓婄殑鐑峰熀鍙?/span>鑺冲熀纾蜂互鍙婁晶閾句簹纾洪叞鑳虹粨鏋勫浜庣ǔ瀹?/span>閽?/span>娲绘�т腑蹇?/span>锛?/span>鎻愰珮鑱氬悎鍙帶鎬ч兘鏄潪甯搁噸瑕佺殑銆?/span>
鍩轰簬浠ヤ笂鐨勫疄楠岀粨鏋滐紝浣滆�呮彁鍑轰簡濡?/span>鍥?/span>3鐨勬満鐞嗭紝鍦ㄨ仛鍚堣捣濮嬬殑寮曞彂闃舵锛?/span>[Pd(allyl)Cl]2鍜?/span>Wei-Phos閰嶄綋棣栧厛鍙戠敓閰嶄綅缁忚繃畏3鈭?/span>畏1鐨勮浆鎹㈠舰鎴愭椿鎬х墿绉?/span>A锛岄殢鍚庣幆涓欑儻鍗曚綋杩涜閰嶄綅褰㈡垚閽?/span>鐗╃B锛岀揣鎺ョ潃鐑笝鍩?/span>鍙戠敓杩佺Щ鎻掑叆褰㈡垚鐢辩幆涓欑儻涓?/span>-C=O鐨勬哀鍘熷瓙绋冲畾鐨勪腑闂翠綋C锛屽湪閾惧闀块樁娈甸�氳繃鐜笝鐑崟浣撲笌缇板熀姘у師瀛愮殑閰嶄綋浜ゆ崲浣滅敤淇濊瘉浜嗙幆涓欑儻鍗曚綋鐨勫彲鎺ц仛鍚堬紝浠庤�屾姂鍒朵簡閾捐浆绉诲拰閾剧粓姝㈣繃绋嬶紝鏈�鍚庨�氳繃鐚濈伃寰楀埌鑱氬悎鐗╂垨鑰呴噸鏂板紩鍙戞柊鐨?/span>鑱氬悎杩囩▼浠庤�?/span>浜х敓宓屾鑱氬悎鐗┿�?/span>
鍥?nbsp;3 閽?/span>鍌寲鐨?/span>鐜笝鐑彲鎺?/span>鍔犳垚鑱氬悎鍙嶅簲鏈虹悊
鐩稿叧鐮旂┒鎴愭灉浠?/span>鈥?/span>Palladium-Catalyzed Living/Controlled Vinyl Addition Polymerization of Cyclopropenes鈥?/span>涓洪鍙戣〃鍦?/span>Journal of the American Chemical Society銆?/span>璁烘枃绗竴浣滆�呬负鍦ㄥ寳浜ぇ瀛﹀寲瀛︿笌鍒嗗瓙宸ョ▼瀛﹂櫌鍚堜綔鍩瑰吇鐨勫唴钂欏彜澶у鍖栧鍖栧伐瀛﹂櫌纭曞＋鐮旂┒鐢熷紶娉介箯锛?/span>鍖椾含澶у鍖栧瀛﹂櫌鐜嬪墤娉?/span>鏁欐巿涓鸿鏂?/span>閫氳浣滆�呫�?/span>姝?/span>椤?/span>宸ヤ綔寰楀埌鍖椾含鍒嗗瓙绉戝鍥藉鐮旂┒涓績鐨勬敮鎸併�?/span>
鍘熸枃閾炬帴锛?/span>//pubs.acs.org/doi/10.1021/jacs.1c09071