Silacyclopropanes Anne-Marie D echert Dechert June 25, 2008
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1 lacyclopropanes Anne-Marie Dechert June 25, 2008
2 utline istory Synthesis eactions of lacyclopropanes Applications to Synthesis Summary/Conclusion
3 Prior Attempts oberts, J.; Dev, S. J. Am. Chem. Soc. 1951, 73, Tang, Y.; Gennaro, G.; Su, Y. J. Am. Chem. Soc. 1972, 94, 4357.
4 First Isolated lacyclopropane Seyferth, D.; Lambert, D. J. Am. Chem. Soc. 1972, 94, Seyferth, D.; Annarelli, D. J. Am. Chem. Soc. 1975, 97,
5 ther Isolated lacyclopropanes Seyferth, D.; Annarelli, D. J. Am. Chem. Soc. 1975, 97, Mollere, P.; offman,. J. Am. Chem. Soc. 1975, 97,
6 Synthesis of lacyclopropanes h short coming: siliranes generated under these conditions are unstable giving rise to isomeric products tal diated lylene Transfer 1. AgTf (5-10 mol%) toluene, 2h, C 2. TMEDA Tf t Bu [Ag] Ln(Ag)Tf Tf [Ag] Tf [Ag] Ishikawa, M.; Kumada, M. J. rganomet. Chem. 1972, 42, 325. Cirakovic, J.; Driver, T.; Woerpel, K. J. Am. Chem. Soc. 2002, 124, 9370.
7 Synthesis of lacyclopropanes Thermal generation of silylenes C 6 D 6, C Broad functional group tolerence, increased yields Cannot be used for cyclohexenes or 1,1 disubstituted alkenes Generation of di-tert-butylsilenoid by lithium reduction of 2 Cl 2 2 Cl 2 Li 0 =,92:8ds = ipr, 96:4 ds ipr P 2 Cl 2 Li 0 ipr P Cl Li ipr Investigated the influence of an ether substitutuent on the reaction. Ether functionality does not direct silacyclopropanation. ot as broad of a scope as the thermal reaction. Driver, T.; Franz, A. Woerpel, K. J. Am. Chem. Soc. 2002, 124, 6524.
8 eactions of lacyclopropanes: Insertions C Seyferth, D.; Duncan, D.; Shannon, M. rganometallics. 1984, 3, 579. A PhC Ph Ph B C D Ph E Ph silirane conditions 1B 1C 1D 1E trans A C Stereochemically and regiochemically defined insertions of aldehydes utcome is dictated by reaction conditions Further elaborated into 1,3 diols cis A C trans A 25% K/ 18-crown cis A 10% / 18-crown <1 <1 Ph Cs. 2 n-bu 4 F Ph - Ar Ar - Bodnar, P.; Palmer, W.; Shaw, J.; Smitrovich, J.; Sonnenberg, J.; Presley, A.; Woerpel, K. J. Am. Chem. Soc. 1995, 117, Bodnar, P.; Palmer, W.; idgway, B.; Shaw, J.; Smitrovich, J.; Woerpel, K. J. rg. Chem. 1997, 62, Ar Ph
9 eactions of lacyclopropanes: Insertions Shaw, J.; Woerpel, K. J. rg. Chem. 1997, 62, 442. guyen, P.; Palmer, W. Woerpel, K. J. rg. Chem. 1999, 64, 1843.
10 eactions of lacyclopropanes: Insertions tal catalyzed Insertion reactions of formamides are stereospecific 10% CuI C 2 Cl 2-78 to 22 o C >93:7 diastereoselectivity 10% CuI C 2 Cl 2-78 to 22 o C one stereoisomer 10% CuI X Cu X Cu Franz, A.; Woerpel, K. J. Am. Chem. Soc. 1999, 121, 949.
11 eactions of lacyclopropanes: Imines evarez, Z.; Woerpel, K. rg. Lett. 2007, 9, 3773.
12 eactions of lacyclopropanes: Imines 1 2 AgTf (5-10 mol%) electrocyclization electrocyclization 1 2 Y Y 3 AgTf (5-10 mol%) Y 2 i-pr i-pr 1 2 PhC AgTf (1 mol %) 3 C Pd(PPh 3 ) 4 (1 mol%) i-pr Ph i-pr evarez, Z.; Woerpel, K. rg. Lett. 9, Pd 1 L 2 Pd(0)L 2 3 L 2 Pd
13 Interesting Transformations of lacyclopropanes oward, B.; Woerpel, K. rg. Lett. 2007, 9, 4651.
14 Interesting Transformations of lacyclopropanes Cleary, P.; Woerpel, K. rg. Lett. 2005, 7, Peng, Z.; Woerpel, K. rg. Lett. 2001, 3, 675.
15 Interesting Transformations of lacyclopropanes Cleary, P.; Woerpel, K. rg. Lett. 2005, 7, Peng, Z.; Woerpel, K. rg. Lett. 2001, 3, 675.
16 Interesting Transformations of lacyclopropanes () 2 ClS 2 C; Cl () 2 () 2 () 2 () 2 2 C S2 Cl cyclization, acid catalyzed hydrolysis () 2 2 S 2 Cl [1,2]- shift 2 () 2 S 2 Cl B 2 () 2 S 2 Cl Cleary, P.; Woerpel, K. rg. Lett. 2005, 7, Peng, Z.; Woerpel, K. rg. Lett. 2001, 3, 675.
17 Application To Total Sythesis: (+/-)-Epi-Stegobinone Female-produced sex pheromone of the drugstore beetle and the furniture beetle eadily isomerizes to epi-stegobinone, which is a repellent to the male species PG ' 1' 2 Et Et Calad, S.; Cirakovic, J.; Woerpel, K. J. rg. Chem. 2007, 72, 1027.
18 Synthesis AgCCF 3 (1-2 mol %) C, CuI CuS 4 (aq), Ac 2 74% X Cu C X Cu B Ac 3 Et SnBr 4 3 Et 97:2:1 dr Et 1. Ph 3 PC 3 Br n-buli, 79% 2. Ph 2 C() K,CsF,94% Et Calad, S.; Cirakovic, J.; Woerpel, K. J. rg. Chem. 2007, 72, 1027.
19 Completed Synthesis Calad, S.; Cirakovic, J.; Woerpel, K. J. rg. Chem. 2007, 72, 1027.
20 Conclusion There are several ways to synthesize silacyclopropanes Photochemical trapping of silylenes tal mediated transfer of silylenoids Thermal generation of silylenes Lithium assisted generation of silenoids through α-elimination Aldehydes, formamides, isocyanides, and imines all undergo insertion reactions with silylcylcopropanes Products of insertions between silylcyclopropanes can be manipulated to form 1,3 diols, enantioenriched α-hydroxy carboxylic acids (with 2 contiguous stereocenters), and various 5 membered rings eactions of silacyclopropanes have been applied to several syntheses including the total synthesis of (+/-)-Epi-Stegobinone
21 Further eading mini i review: Franz, A.; Woerpel, K. Acc. Chem. es. 2000, 33, 813. transition state structures/ explanations for attack on 5-membered ring oxacarbenium ions: Bear T.; Shaw, J.; Woerpel, K. J. rg Chem 2002, 67, Larsen, C.; ideway, B.; Shaw, J.; Woerpel, K. J. Am. Chem. Soc.1999, 121, Ireland Claisen methodology: Calad, S.; Woerpel, K. J. Am. Chem. Soc. 2005,, 127,, 2046.
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