Total Synthesis of Gracilioether F: Development and Application of Lewis Acid Promoted Ketene-Alkene [2+2] Cycloadditions and Late Stage C-H Oxidation
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1 Total Synthesis of Gracilioether F: Development and Application of Lewis Acid Promoted Ketene-Alkene [2+2] ycloadditions and Late Stage - xidation hristopher M. Rasik and M. Kevin Brown Angew. hem. Intd. Ed. 2014, 53, 1-6 Gracilioether F Mike Wipf Group Page 1 of 18 12/6/2014
2 Introduction Isolated from marine sponge Plakinastrella mamillaris in 2012 o known biological activity ther members show antimalarial activity o prior syntheses of any members Me 2 Gracilioether E Gracilioether F Me 2 Gracilioether G Tetrahedron 2012, 68, Gracilioether Gracilioether I Me 2 Gracilioether J Mike Wipf Group Page 2 of 18 12/6/2014
3 Retrosynthesis Gracilioether F - oxidation [] [2+2] + Angew. hem. Intd. Ed. 2012, 68, Mike Wipf Group Page 3 of 18 12/6/2014
4 Previous Generation of Ketenes in Presence of Lewis Acids + l R 2 Til 4. TF 2 (cat.) DIPEA, 2 l 2 R 2 = Me, l, R 2 = Me,, protected heteroatom LA R 3 R 2 R 3 R + Br R = Alkyl, Aryl Alkynyl Me ipr Bn Al Tf Tf ipr DIPEA, 2 l to 90% yield >90% ee, >7:1 d.r. Me R J. Am. hem. Soc. 1999, 121, rg. Lett. 2000, 2, Mike Wipf Group Page 4 of 18 12/6/2014
5 Pd-Mediated Ketene-Alkene [2+2] Pd(II) R Br Me, up to 93%, >10:1 d.r. R Br R = Alkyl Significant improvement in yield over thermal reaction pposite diastereomer of thermal reaction Very limited scope Tetrahedron. 2001, 57, Mike Wipf Group Page 5 of 18 12/6/2014
6 Previous [2+2] Ketene-Alkene ycloadditions R 2 l 3 2 l 2 R 2 All 2 2 l 2, -78 to 22 o n n R 2 = Alkyl, Aryl R 2 = Aryl 59-91% yield 5:1-19:1 d.r. Thermal Pathway Sc(Tf) 3, Zn(Tf) 2, Fel 3, Snl 4, Sil 4, Bl 3, AgTf, Sn(Tf) 2, Mg(l 4 ) 2, utf, Agl 4, In(Tf) 3, AlMe 3 all gave no product LA pposite diastereomer from thermal LA [2+2] Lewis acid Pathway J. Am. hem. Soc. 2013, 135, Mike Wipf Group Page 6 of 18 12/6/2014
7 Previous [2+2] Ketene-Alkene ycloadditions R 2 l 3 2 l 2 R 2 All 2 2 l 2, -78 to 22 o n n R 2 = Alkyl, Aryl R 2 = Aryl 59-91% yield 5:1-19:1 d.r. Thermal Pathway Lewis acid Pathway LA LA J. Am. hem. Soc. 2013, 135, rg. Lett. 2014, 16, Mike Wipf Group Page 7 of 18 12/6/2014
8 Previous [2+2] Ketene-Alkene ycloadditions Alkene from less hindered side in thermal reaction n Lewis acid has steric clash with ; leads to selectivity 3 All 2 l R Rotational barrier R 2 l 2 for -ketene bond 2 l 2, -78 to reduced 22 o from R 2 n to 1.7 kcal/mol = Alkyl, Aryl R 2 = Aryl 59-91% yield 5:1-19:1 d.r. Thermal Pathway Lewis acid Pathway LA LA J. Am. hem. Soc. 2013, 135, rg. Lett. 2014, 16, Mike Wipf Group Page 8 of 18 12/6/2014
![Previous [2+2] Ketene-Alkene ycloadditions Alkene from less hindered side in thermal reaction Lewis acid has steric clash with ; leads to selectivity Rotational barrier for -ketene bond reduced from](/docs-images/94/118539468/images/9-1.jpg "3.6 to 1.7 kcal/mol All 2 2 l 2, -78 to 22 o 69% yield 10:1 d.r. opposite diastereomer J. Am. hem. Soc. 2013, 135, 1673-1676 rg. Lett.")
9 Previous [2+2] Ketene-Alkene ycloadditions Alkene from less hindered side in thermal reaction Lewis acid has steric clash with ; leads to selectivity Rotational barrier for -ketene bond reduced from 3.6 to 1.7 kcal/mol All 2 2 l 2, -78 to 22 o 69% yield 10:1 d.r. opposite diastereomer J. Am. hem. Soc. 2013, 135, rg. Lett. 2014, 16, Mike Wipf Group Page 9 of 18 12/6/2014
10 Retrosynthesis Gracilioether F - oxidation [] [2+2] + Angew. hem. Intd. Ed. 2012, 68, Mike Wipf Group Page 10 of 18 12/6/2014
11 Development of [2+2] for Gracilioether F R l 3 2 l 2 R 2 AlMe 3 2 l 2, -78 to 22 o 4 Incorrect Diastereomer R 2 1 <2% yield l l 2 42% yield 7:1 d.r. l 3 61% yield 3:1 d.r. Angew. hem. Intd. Ed. 2012, 68, Mike Wipf Group Page 11 of 18 12/6/2014
12 ew Strategy for [2+2] Lewis Acid promoted [2+2] 7 Alkylation 8 9 l AlMe 3, DIPEA 2 l 2, -78 to -45 o 69%, 8:1 d.r. 10 KMDS, then I TF, -78 to 22 o 91%, >20:1 d.r. 11 Angew. hem. Intd. Ed. 2012, 68, Mike Wipf Group Page 12 of 18 12/6/2014
13 ew Strategy for [2+2] Lewis Acid promoted [2+2] 7 Alkylation 8 9 l AlMe 3, DIPEA 2 l 2, -78 to -45 o 69%, 8:1 d.r. 10 KMDS, then I TF, -78 to 22 o 91%, >20:1 d.r. 11 Angew. hem. Intd. Ed. 2012, 68, Mike Wipf Group Page 13 of 18 12/6/2014
14 Synthesis 3, Me/ 2 l 2, -78 o then ab 4, 0 o, 18% 2. Me 2 uli. LiI, 2-45 to 22 o % 1. Tsl, pyridine 0 to 22 o 9, AlMe 3, DIPEA 2 l 2, -78 to -45 o 65%, >20:1 d.r. AlMe 3 7 KMDS, then I TF, -78 to 22 o 8 2 steps 9 l Angew. hem. Intd. Ed. 2012, 68, Mike Wipf Group Page 14 of 18 12/6/2014
15 Synthesis (cont d.) 2 2, a Me then al 61%, >20:1 d.r. 2, a 2 P 4 t-bu, isobutylene 83% , 2 l 2,-78 o - oxidation Gracilioether F Angew. hem. Intd. Ed. 2012, 68, Mike Wipf Group Page 15 of 18 12/6/2014
16 - xidation Development 11 onditions Gracilioether F F 3 TFD Entry onditions Yield (%) RSM (%) * Rul 3, KBr 3, pyridine Me/ 2 <2 --- TFD, 2 l 2, -45 to 22 o <2 >90 Fe(PDP) (20 mol%), 2 2,Me 9 48 Fe(Ac) 2, 2 2,Me <2 ~80 Mn(Ac) 2, 2 2,Me <2 ~80 u(ac) 2, 2 2,Me u(ac) 2, 2 2,Me, 0 o u(ac) 2, 2 2,Me, 0 o <2 >90 3 Fe 3 Fe(PDP) *using Me ester of 11 Angew. hem. Intd. Ed. 2012, 68, Mike Wipf Group Page 16 of 18 12/6/2014
17 - xidation Development 11 onditions Gracilioether F F 3 TFD Entry onditions Yield (%) RSM (%) * Rul 3, KBr 3, pyridine Me/ 2 <2 --- TFD, 2 l 2, -45 to 22 o <2 >90 Fe(PDP) (20 mol%), 2 2,Me 9 48 Fe(Ac) 2, 2 2,Me <2 ~80 Mn(Ac) 2, 2 2,Me <2 ~80 u(ac) 2, 2 2,Me u(ac) 2, 2 2,Me, 0 o u(ac) 2, 2 2,Me, 0 o <2 >90 3 Fe 3 Fe(PDP) *using Me ester of 11 Angew. hem. Intd. Ed. 2012, 68, Mike Wipf Group Page 17 of 18 12/6/2014
18 onclusions Gracilioether F was synthesized in 8 steps in 0.35% yield Features a unique Lewis acid promoted ketene-alkene [2+2] cycloaddition and a late stage - oxidation Yield is disappointing - oxidation is very impractical Mike Wipf Group Page 18 of 18 12/6/2014
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