【正文】 。sser Angew. Chem., Int. Ed. Eng. 1966, 5, 126. ? Stabilized Ylides Stabilized ylides are solid。 ? The position of the double bond is unambiguous. ? Features OM e M g I1 )2 ) H+H O M eC H 2P h 3 P = C H 2 H 2 OC H 3 C H 2+? Representative Examples Example 1 Example 2 Example 3 Example 4 ? Mechanism [2 + 2] cycloaddition. P h 3 P C H 2 C H 3 + E t C H O +D M F + L iC 6 H 6 + L iZ / E9 6 / 4 0 / 1 0 0P h C H = C H E t P h 3 P O? Influence of solvent on the selectivity ? Activity and stereoselectivity of Yild P h 3 P C H R R = a l k y l ， E D GR =R = E W Ga l k e n y l o r a l k y n y lS t e r e o s e l e c t i v i t yZ ( m a j o r )Z / E ( m i x t u r e )E ( m a j o r )S t a b i l i t yi n c r e a s e? Schl246。R RR 39。 ( H )R + C HR 39。R C H 2 C O 2 E tC O 2 M eC O 2 M eNL iC O 2 M eO5. Dickmann Condensation ( C H 2 ) nC O 2 E tC O 2 E t B :( C H 2 ) n 1OC O 2 E t分 子 內(nèi) C l a i s e n 縮 合 反 應(yīng)Chapter 3 Formation of CarbonCarbon Doule Bonds 1. ?Elemination reactions （ ?消去反應(yīng) ） C CH XC C + H XX = O H , O C O R , 鹵 素 , O S O 2 A r , N + R 3 , S + R 2 e t a l .R e g i o s e l e c t i v i t yS a y t z e f f r u l eH o f m a n n r u l eX = O H , O C O R , 鹵 素 , O S O 2 A r ,X = N + R 3 , S + R 2S t e r e o s e l e c t i v i t yS y n e l i m i n a t i o nA n t i e l i m i n a t i o nH o f m a n n e l i m i n a t i o n sS a y t z e f f e l i m i n a t i o n sA n t i e l i m i n a t i o nI. The Synthetic Methods of Alklenes 2. Pyrolytic syn eliminations（順式熱消去反應(yīng) ） C CH OC C + R C O 2 HRO3 0 0 ~ 5 0 0 o CApplications: Synthesis of terminal alkenes from primary acetates Disadvantages: High reaction temperature C H 3 C H 2 C H 2 C H 2 O C O C H 3 5 0 0 o CN2C H 3 C H 2 C H = C H 2 1 0 0 %C CH OC C + H S C S RS RS1 0 0 ~ 2 0 0 o COCope reaction C CH N R 2C C + R 2 N O HO1 0 0 ~ 2 0 0 o CChugave reaction 反應(yīng)條件比對應(yīng)的酯熱消去溫和。 t o t a l y i e l d 9 6 %B e n j a m i n L i s t . J . A m . C h e m . S o c . 2 0 0 0 , 1 2 2 ( 3 8 ) , 9 3 3 6 7The Direct and Enantioselective, OnePot, ThreeComponent, CrossMannich Reaction of Aldehydes Angew. Chem. Int. Ed. 2022, 42, 3677 –3680 Y. Hayashi,W. Tsuboi, I. Ashimine, T. Urushima,Dr. M. Shoji Department of Industrial Chemistry, Faculty of Engineering Tokyo University of Science, Kagurazaka Threeponent Mannich reaction with various acceptor aldehydes Nmethyl2pyrrolidinone (NMP) Threeponent Mannich reaction with various donor aldehydes. 4. Claisen Condensation ? General Scheme 2 R C H 2 C O 2 E tB :R C H 2 C C H C O 2 E tRO? Mechanism R C H C O E tOB :HR C H C O E tO+ R C H COHO E tR C H COHO E tR C H C O E tO E t OR C H2C C H C O2E tRO ? 一種酯的自身縮合 ? Scope of application ? 一種含 ?H 的酯與一種不含 ?H的酯之間的縮合 ? Examples NC O 2 E t + N a HNC O C H C O 2 E tE tE t C H 2 C O 2 E tC O 2 E tC O 2 E t+ P h C H 2 C O 2 E tE t O N aE t O HC O C H C O 2 E tP hC O 2 E t 1 7 5 o C C OC HP hC O 2 E tC O 2 E t? Directed Claisen condensation L D A R C H C O 2 E t R 39。e e : 7 3 9 6 %OD M S OO+L P r o l i n e3 5 m o l %r . t .C H O N H 2O M e+1 2 h5 0 %N H P M PR1R2R2R1a . R1= H , R2= M e , 9 9 % e e 。 Notz, W.。 Watanabe, .。 (f) Co180。 Betancort, J. M.。 Notz, W.。 (e) Co180。 Shibasaki, M. Tetrahedron 1999, 55, 8857。 (c) Yamasaki, S.。 Gathergood, N.。 Barbas, C. F., III Tetrahedron Lett. 2022, 42, 199。 Bui, T.。 Manabe, K. J. Am. Chem. Soc. 2022, 124, 5640. (a) Notz, W.。 Lectka, T. J. Am. Chem. Soc. 2022, 124, 67. (g) Kobayashi, S.。 Ryzhkov, L.。 Dudding, T.。 Young, B.。 Leckta, T. J. Am. Chem. Soc. 1998, 120, 4548。 Yong, B.。 Kobayashi, S. J. Am. Chem. Soc. 1997, 119, 2060。 (d) Ishitani, H.。 Hattori, K.。 (c) Ishihara, K.。 Ueno, M.。 Sodeoka, M. J. Am. Chem. Soc. 1999, 121, 5450。 HHN H M eM eOH C H ONM eOM eExample 2 Example 1 O+ H C H O + H N M e 2 H C l.ON M e2OO E tO OM i c h a e l a d d i t i o n OC O2E tH3COA l d o l r e a c t i o nC O2E tO1 ) O H2 ) H / C O2+ O? Development: Asymmetry Mannich Reaction ? Lewis acidcatalyzed asymmetric Mannich reactions (a) Fujii, A.。% e e : 8 3 9 6 %e n d o e x oe n d o : e x o : 8 0 : 2 0 9 9 : 1% e e : 9 0 9 9 %y i e l d : 6 6 9 8 %J . A m . C h e m . S o c . 2 0 0 0 , 1 2 2 ( 1 7 ) , 4 2 4 3 4 2 4 4J . A m . C h e m . S o c . 2 0 0 0 , 1 2 2 ( 4 0 ) , 9 8 7 4 9 8 7 5+2 0 m o l % A H C l O4 2 0oC2 0 m o l % A T F Ay i l e d : 7 4 8 7 % 。G W EC HRE W G , E W G 39。 C HCR 39。 RE W G 39。 LuoTing Yu,? Xin Cui,? LiuZhu Gong,*,? AiQiao Mi,?YaoZhong Jiang,? and YunDong Wu* Key Laboratory for Asymmetric Synthesis and Chirotechnology of Sichuan Province, Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, 610041, China, College of Chemical Engineering, Sichuan UniVersity, Chengdu, 610065, China, and State Key Laboratory of Molecular Dynamics and Stable Structures, College of Chemistry and Molecular Engineering, Peking UniVersity, Beijing, 100871, China 2. Michael Addition Reaction E W GC H 2R R 39。 A r C H OROR 39。 % e e : 6 7 9 9 %C a r l o s F . B a r b a s I I I e t . a l . J . A m . C h e m . S o c . 2 0 0 0 , 1 2 2 ( 3 0 ) , 7 3 8 6 7P r o l i n e C a t a l y z e d A s y m m e t r i c A l d o l R e a c t i o n s b e t w e e nHOOO O H+L P r o l i n e1 0 2 0 m o l %