Ring Opening/Fragmentation of Dihydropyrones for the Synthesis of Homopropargyl Alcohols
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1 ig peig/fragmetatio of Dihydropyroes for the Sythesis of Homopropargyl Alcohols ' 1 '-M X 1 '-M 1 H X = C Tf X = Jumreag Tummator ad Gregory B. Dudley J. Am. Chem. Soc. 2008, ASAP Curret Literature Presetatio Abhisek Baerjee Wipf Group Mar Abhisek Wipf Group Page 1 of 14 3/30/2008
2 The Crossover eactio The Eschemoser-Taabe Fragmetatio ' ' H -N 2 ' NNHTs NNTs -TsH Eoe Formatio from Viylogous Acid Ester 1 3 H 3 -M 1 H H Tadem Additio/Fragmetatio of Viylogous Acyl Triflates 1 '-M ' M -MTf ' Tf Tf Dudley et al. J. Am. Chem. Soc. 2006, 128, 6499 Abhisek Wipf Group Page 2 of 14 3/30/2008
3 Tadem Nucleophilic Additio/C-C Bod Fragmetatio eactios of Viylogous Acyl Triflates NH' 'NHLi '-M (M= Li, MgX) ' Tf H LiBHEt 3 ' Li EWG (stabilized carbaios) Dudley et al. J. Am. Chem. Soc. 2006, 128, 6499 Abhisek Wipf Group Page 3 of 14 3/30/2008
4 Sythesis of Acetylee tethered Ketoes Tf Tf =, 65% = Bu, 63% =, 96% = Bu, 52% Tf =, 79% = Bu, 39% Tf =, 61% = Bu, 14% eactio Coditios: Viylogous acyl triflate (0.55 mmol), Li (0.50 mmol) i solvet (2 ml) =, THF; = -Bu, Toluee ther Aryl Grigard or Lithium reaget such as o-, m-, p-()c 6 H 4 -MgBr. ther Alkyl Lithium reaget such as i-prli, t-buli, Li. Yields suffer with reactive ad hidered ucleophilic reagets. Bu Bu H 56% 64% alkyyl lithium reaget viyl lithium reaget 77% excess lithium reaget (2.2 equiv.) Dudley et al. J. Am. Chem. Soc. 2006, 128, 6499 Abhisek Wipf Group Page 4 of 14 3/30/2008
5 Sythesis of Acetylee tethered 1,3-Diketoes Li EWG Tf THF Stoichiometry: Triflate (1 equiv.); Preucleophile (2.6 equiv.), LiHMDS (2.2 equiv.) Et S P CN 85% 42% 88% 53% 21% 22% 95% ot isolated 45% 79% Dudley et al. J. Am. Chem. Soc. 2006, 128, 6499 Abhisek Wipf Group Page 5 of 14 3/30/2008
6 Sythesis of Acetylee tethered Alcohols LiBHEt 3 (2.2 equiv.) H Tf THF H H H H H H 73% 62% 56% 30% 50% 63% Dudley et al. J. Am. Chem. Soc. 2006, 128, 6499 Abhisek Wipf Group Page 6 of 14 3/30/2008
7 Sythesis of Acetylee tethered Amides Tf 'NH 2, -BuLi THF NH' NHPr NH i Pr NH t Bu NHB NH 91% 87% 49% 91% 79% NH NH NH NH NH 84% 59% <7% 88% 20% secodary amies resulted i decompositio of the triflate Dudley et al. J. Am. Chem. Soc. 2006, 128, 6499 Abhisek Wipf Group Page 7 of 14 3/30/2008
8 Sythesis of Homopropargyl Alcohols Homopropargyl alcohols key buildig block for sythesis of Polyketides ad macrolides H '-M Tf 2 2 Marshall et al. Chem. ev. 1996, 96, 31 Abhisek Wipf Group Page 8 of 14 3/30/2008
9 Sythesis of Chiral Dihydropyroes Hetero Diels-Alder Approach: TMS i) 5 mol% A/B, Cu(Tf) 2 + H Toluee, -78 C ii) TFA t-bu N H H ' A: ' = t-bu B: ' = Adametyl Feg et al. J. rg. Chem. 2006, 71, 4141 Author s Approach: 1 2 CH 3 i) NaH, THF ii) -BuLi, 0 C iii) 3 4 iv) aq. NaH Tf 2, Et 3 N CH 2 Cl 2, -78 C % 73-98% 1 Tf Imbroisi et al. Bioorg. d. Chem. 2004, 12, 865 Abhisek Wipf Group Page 9 of 14 3/30/2008
10 Decompositio of DHP Triflate Uder Various Coditios Tf 2, Et 3 N CH 2 Cl 2, -78 C Tf -M (2 equiv.) Solvet -78 C to rt H Toluee is better solvet tha THF Grigard Nucleophiles outperformed orgaolithiums thylmagesium bromide is optimal choice Dudley et al. J. Am. Chem. Soc. 2008, 130, ASAP Abhisek Wipf Group Page 10 of 14 3/30/2008
11 Postulated eactio Pathway Tf '-M (2 equiv.) (aqueous workup) 1 H ' ' ' M 1 Tf 1 ' Tf M 4 1 Tf 2 3 M ' M ' Dudley et al. J. Am. Chem. Soc. 2008, 130, ASAP Abhisek Wipf Group Page 11 of 14 3/30/2008
12 Decompositio of DHP Triflates with MgBr Tf MgBr (2 equiv.) Toluee -78 C to rt H H H H H Aryl Substituets: quat. Br 99% 95% 92% electro poor electro rich H H H H 84% quat. 85% 91% liear brached tertiary Dudley et al. J. Am. Chem. Soc. 2008, 130, ASAP Abhisek Wipf Group Page 12 of 14 3/30/2008
13 Decompositio of Substituted DHP Triflates 1 Tf MgBr (2 equiv.) Toluee -78 C to 60 C 1 H H H B H 1 = H; 2 = H; 3 = CH 2 CH 2 ; 4 =, 82% gemial disubstitutio, tertiary alcohol 1 = ; 2 = H; 3 = ; 4 = H, quat. iteral alkyes 1 = B; 2 = H; 3 = ; 4 = H, 92% H H H 1 = H; 2 = ; 3 = Cy; 4 = H, 76% 1 = H; 2 = ; 3 = H; 4 = Cy, 78% B 1 = H; 2 = B; 3 = H; 4 =, 83% cis DHP to sy HPA tras DHP to ati HPA Dudley et al. J. Am. Chem. Soc. 2008, 130, ASAP Abhisek Wipf Group Page 13 of 14 3/30/2008
14 Summary C-C bod cleavig fragmetatio reactio iduced by the additio of various ucleophiles to cyclic viylogous acyl triflates produces acyclic acetyleic compouds. Nucleophilic additio of methylmagesium bromide to 5,6-dihydro-2-pyroe (DHP) iitiates a rig opeig/fragmetatio process to furish homopropargyl alcohols. This stereospecific strategy provides chiral homopropargyl alcohols that may be difficult to access by other meas. Abhisek Wipf Group Page 14 of 14 3/30/2008
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