Operating mechanisms: Useful articles:
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1 Useful articles: Fairlamb, ACIEE, 2004, Aubert et al., Chem. Rev., 2002, 813. Fletcher et al., J. Chem. Soc., Perkin 1, 2000, Fürstner et al., Chem. Eur. J., 2004, Kozmin et al. Adv. Synth. Catal., 2006, Lloyd-Jones, BC, 2003, 215. Toste et al., Nature, 2007, 395. jima et al., Chem Rev., 1996, 635. Trost et al., Acc. Chem. Res., 1990, 34. Trost et al., Chem. Rev., 2001, Trost et al., Synlett, 1998, 1. perating mechanisms: - A) The Metallocyclopentene Pathway - β- elimination - Reductive elimination - Electrophilic cleavage - B) The π-allylmetal Pathway - C) The Vinylmetal Pathway
2 General mechanisms for enynes: 1. Metallopentene -> β-elimination - Major and fastest pathway. - Reguires a vacant coordination site on the metal and cis relationsship to eliminated proton. - Generates 1,3- or 1,4-diene from enyne: - Six metals usually applied: Pd, Ru, Rh, Co, Ir & Ti. - Pd: 1,3-diene formed when allylic oxygen present and 1,4-diene formed when homoallylic oxygen present. Steric congestion favors 1,3-dienes. - Interesting switch: Aubert et al., Chem. Rev., 2002, 813. Trost et al., JACS, 1985, 1781; 1991, 636 & 1994, 4255.
3 - Cobalt mediated a number of distinct cyclizations: Pauson-Khand, Intramolecular Nicholas reaction and cyclotrimerization. - Enynes react with Co to form five-membered rings regardless of the length of the tether: This can be stopped by a quarternary carbon next to ene: - Cobalt can also mediate a Conia ene-type reaction: Stammler et al., Synlett, 1994, Metallopentene -> Reductive-elimination - When β-elimination is retarded reductive elimination becomes possible. - The intermediate bicyclic cyclobutene of the formal [2+2] can be isolated, where thermal opening of cyclobutene isn t possible. - Usually mediated by Pd, Pt or Ru. Fletcher et al., Perkin 1, 2000, Aubert et al., TetLett., 1996, 7353 & Chem. Eur. J., 2001, 3517.
4 The Pauson-Khand reaction DMAD, P(-o-tol) 3, DCE - EWG on the alkyne favors metahesis along with severe steric congestion. Trost & Trost, JACS, 1991, Ruthenium carbene complexes are well known to mediate similiar reactions eg. olefin metathesis. 3. Metallopentene -> Electrophilic cleavage - ccurs when no vacant coordination sites are present on the metal hence no β-elimination. - Competes with reductive elimination with one or two electrophiles. - Typically mediated by metals such as Ti, Co and Zr. Khand, Pauson et al., Perkin 1, 1973, Reaction with different electrophiles: The metallopentene can react directly with electrophiles or be transmetalleted. Negishi et al., JACS, 1998, 5345.
5 The π-allylmetal Pathway - Cyclization of enedienes generates a π-allylic complex with typically Fe or Pd. - Pd can in addition react by preforming the π-allyl complex when a suitable leaving group is in the allylic position - known from the Tsuji-Trost reaction. Direct cyclization: - The two metal-carbon bonds can be differentiated with carbon electrophiles depending on the metallocycle: Hill et al., rganometallics, 1993, Urabe et al., JC, 1996, Negishi et al., TetLett, 1994, 695. Takacs et al., TetLett., 1990, 2865; TetLett., 1993, 6219 & JC; 1994, 6928.
6 Cyclization after preformed allylmetal-complex: - The cyclized intermediate can be intercepted or allowed to β-eliminate. - Starting from tin-hydride the tin can be placed on the other branch. The Vinylmetal Pathway - Addition of R-M-species across an alkyne leads to a vinylmetal intermediate capable of reacting with the alkene. - M being Pd, Ru(enyne metathesis) and R being H, SnR 3 or BR 2. - The vinylmetal can be genereated from a carbonhalogen bond(heck reaction) Trost et al., JACS, 1994, 4268; TetLett., 1989, 651. Lautens et al., JC, 2000, 671. nozawa et al., rganometallics, 1997, Mori et al., rganometallics, 2001, 1907.
7 Gold(I) by another mechanism? Hydrogen shift - Supported by deuterium-labelling and alkyl-shift. M. Luzung, J.P. Markham, F.D. Toste, JACS, 2004,
8 Application to synthesis: Total Synthesis of Platensimycin E E Ts N Pd 2 (dba) 3 *CHCl 3, PPh 3, PhH, AcH, 80 ºC, 40%. E E NTs K.C. Nicolaou, A. Li, E.J. Edmonds, ACIEE, 2006, 7086 Pd 2 (dba) 3 *CHCl 3, PPh 3, PhH, AcH, 50 ºC, 77%. TBS TBS Ph 2 S Ph 2 S CH 3 Pd 2 (dba) 3 *CHCl 3, SbPh 3, PhH, AcH, 50 ºC, 77 %. CH 3 Trost et al., Synlett, 1998, 1. Trost et al., JACS, 1993, Ph 2 S S2 Ph
9 Asymmetric Total Syntheses of Platensimycin K.C. Nicolaou, E.J. Edmonds, A. Li, G.S. Tria, ACIEE, 2007, 3942
10 Total Synthesis of (+/-)-Salviasperanol E.M. Simmons, R. Sarpong, rg. Lett, 2006, GaCl 3, 50 ºC Me Me 20 mol% GaCl 3, PhH, 4Å MS, 40 ºC, 24 h Me Me
11 Synthesis of (+/-)-Epiglobulol Y. onishi, A.Taniuchi, M. Mori, Y. Sato, Tet.Lett, 2006, % E = CMe H H 8b 11 steps H (+/-)-Epiglobulol
12 Total Synthesis of (-)-Laurebiphenyl B.K. Corkey, F. D. Toste, JACS, 2007, CH a) i) (CCl) 2, DMF ii) LDA, EtAc, 59% b) NaH, 5-iodo-1-pentyne, 51% e) TBSTf, NEt 3 f) 10% A, Et 2, AcH, rt, 96%, 95% ee (91% cat. recovered) I g) Pd(Ac) 2,PPh 3, NEt 3, HCH, DMF, 96%. h) CF 3 C()H, BF 3 *Et 2, DCM, -10 ºC, 48%. I c) NaH, MeI, 80% d )NaH, 42% I H H n) t BuLi, 0.5 eq. CuCN, tetramethylquinone, 51% o) NaH, EtSH, DMF, 150 ºC, 70% Br Me i) LAH j)k 2 C 3, MeI k) DMP, NaHC 3 (81% - 3 steps) l) TsNHNH 2, 73% m)nah, o -dichlorobenzene 160 ºC, 2 min, then Br 2, 68%. Me
13 Total Synthesis of (-)-Pseudolaric Acid B B.M. Trost, J. Waser, A. Meyer, JACS, 2007, steps 62 % TBS I i) Schlosser-wittig olefination ii) TMS-deprotection TBDPS H Mechanism: H 3 steps 84% TMS TBDPS 58%, 53% E 11 mol% Rh CD TBS +, SbF 6 - H 23 mol% +,PF 6 - CH 3 CN Ru NCCH3 CH 3 CN 88% 48%, 15% conjugated diene H TBDPS HC CMe 20 steps TBS H TBDPS TBS H
14 Total Synthesis of the Picrotoxane Sesquiterpenes B.M. Trost, M.J. krische, JACS, 1999, 6131 & (R)-Carvone 6 steps H TBDMS TBDMS 7.4 g Br 10 mol% Pd(Ac) 2 10 mol% dbpp, 10 mol% dpba, DCE, reflux, 21 h, 70 % TBDMS TBDMS Br CH (dpba) PPh 2 Picrotoxinin Picrotin P P H H H (dbpp) H H Methyl Picrotoxate Corianin H H Me
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