有機(jī)反應(yīng)機(jī)理第九章-資料下載頁
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【正文】 效果較鎳好 有機(jī)反應(yīng)機(jī)理 Negishi偶聯(lián)反應(yīng)的特點(diǎn)（續(xù)） Of all the various anometals (Al, Zr, B, Sn, Cu, Zn), anozincs are usually the most reactive in Pdcatalyzed crosscoupling reactions and do not require the use of additives (., bases as in Suzuki cross couplings) to boost the reactivity 有機(jī)鋅的鈀催化偶聯(lián)活性高，不需加助催化劑（如 Suzuki偶聯(lián)需堿作助催化劑） 有機(jī)反應(yīng)機(jī)理 Negishi偶聯(lián)反應(yīng)的特點(diǎn)（續(xù)） Greater functional group tolerance in both coupling partners than in the Kumada crosscoupling where more basic anolithiums and Grignard reagents are utilized as coupling partners 有機(jī)鋅化合物堿性小于格林亞試劑和有機(jī)鋰，官能團(tuán)容忍度較 Kumada偶聯(lián)好 有機(jī)反應(yīng)機(jī)理 Negishi偶聯(lián)反應(yīng)的特點(diǎn)（續(xù)） Other advantages of the use of anozincs include: high reactivity, high regio, and stereoselectivity, wide scope and applicability, few side reactions and almost no toxicity 與 Still偶聯(lián)比較，有機(jī)鋅毒性小于有機(jī)錫 有機(jī)反應(yīng)機(jī)理 Negishi偶聯(lián)合成 天然抗菌藥 ()hectochlorin NSOOH OOSN O A cOOOC lC l1有機(jī)反應(yīng)機(jī)理 Jeannie R. P. Cetusic, Frederick R. Green III, Paul R. Graupner, and M. Paige Oliver. Total Synthesis of Hectochlorin. Org. Lett., 2022, 4(8): 1307~1310 參考文獻(xiàn) (見 41) 有機(jī)反應(yīng)機(jī)理 NSB rO E tOM g B rZ n B r 2 / T H F / ( d p p f ) P d C l 28 9 %N e g i s h i c o u p l i n gNSO E tONSOOH OOSN O A cOOOC lC l1steps有機(jī)反應(yīng)機(jī)理 鹵代烴與有機(jī)錫的偶聯(lián) Stille偶聯(lián)， 1978， J K stille R S n ( a l k y l ) 3 R 1 X P d ( 0 ) / l i g n a d R 1 R+有機(jī)反應(yīng)機(jī)理 Stille偶聯(lián)的機(jī)理 LnPd(0) R 1 Xo x i d a t i v e a d d i t i o nXR1LnPd (II)t r a n s m e t a l l a t i o nR S n ( a l k y l ) 3X S n ( a l k y l ) 3RR1LnPd (II)R1Rr e d u c t i v e e l i m i n a t i o n有機(jī)反應(yīng)機(jī)理 Stille偶聯(lián)反應(yīng)的特點(diǎn) Organostannanes are not sensitive to moisture or oxygen unlike other reactive anometallic pounds The main disadvantages are their toxicity and the difficulty to remove the traces of tin byproducts from the reaction mixture 活性低，對水不敏感，試劑毒性較大 有機(jī)反應(yīng)機(jī)理 Stille偶聯(lián)合成 (+)mycotrienol H OH ON HOO M eOOAn antibiotic 有機(jī)反應(yīng)機(jī)理 參考文獻(xiàn) Craig E M, Michael Y, Jason S, and James S P. Total Synthesis of (+)Mycotrienol and (+)Mycotrienin I: Application of Asymmetric Crotylsilane Bond Constructions. J Am Chem Soc, 1998, 120(17): 41234134 有機(jī)反應(yīng)機(jī)理 T B S OT I P S OIN HOIO M eO M eO M e1 . B u 3 S nS n B u 3P d ( M e C N ) 2 C l 2 / D M F / T H F / E t NiP r 2r . t . , 2 4 h2 . C A N / T H F / H 2 O ( o x i d a t i o n o f t h e a r o m a t i c c o r e )3 . a q . H F / C H 3 C N 5 4 % f o r 3 s t e p sH OH ON HOO M eOO有機(jī)反應(yīng)機(jī)理 Stille羰基化交叉偶聯(lián) 由于有機(jī)錫的活性相對較低，在 CO存在下，可發(fā)生 CO插入的羰基化交叉偶聯(lián) +R 1 S n R 3 R 2 XR 1 R 2OP d ( 0 ) / C O / l i g a n d有機(jī)反應(yīng)機(jī)理 Stille羰基化交叉偶聯(lián)機(jī)理 LnPd(0)XR2LnPd (II)C OXL n P dOR 2(II)R 1 S n R 3X S n R 3R 1L n P dOR 2(II)R 1 R 2OR 2 X有機(jī)反應(yīng)機(jī)理 Stille羰基化交叉偶聯(lián)合成 Cglycosides OOS iOO T I P SI OOS iOO T I P SB u3S n+P d C l2( P P h3)2/ C O ( 5 M P a )5 0oC , 6 5 %OOS iOO T I P SOOS iOO T I P SO有機(jī)反應(yīng)機(jī)理 Jeanneret, V., Meerpoel, L., Vogel, P. CGlycosides and Cdisaccharide precursors through carbonylative Stille coupling reactions. Tetrahedron Lett. 1997, 38, 543546. 參考文獻(xiàn) 有機(jī)反應(yīng)機(jī)理 See you next time
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