A New Strategy for Efficient Synthesis of Medium and Large Ring Lactones without High Dilution or Slow Addition
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1 A ew Strategy for Efficient Synthesis of Medium and Large ing Lactones without High Dilution or Slow Addition BF 3 Et 2 TIPS 2,4,6-collidine n + n+2 ' ' Zhao, W.; Li, Z; Sun, J. J. Am. Chem. Soc ASAP Joshua Sacher 23 March 2013 Josh Wipf Group Page 1 of 11 4/21/2013
2 Macrolactonization 16 H 14 H H H 25 H Me Mycacolide A Ac H CH Exaltolide (perfume musk) Erythromycin A (antibiotic) H Me Me Direct lactonization: Activated acids (Carbodiimides, P-based, Yamaguchi, etc.) Carboxylate attack (Mitsunobu, Iodolactonization, etc.) Indirect formation: CM lefination (Wittig, HWE, Julia) thers (ex: heterocycles, couplings) Parenty, A.; Moreau, X.; iel, G.; Campagne, J.-M. Chem. ev. 2013, 113, P1 Illuminati, G.; Mandolini, L. Acc. Chem. es. 1981, 14, IG SIZE Josh Wipf Group Page 2 of 11 4/21/2013
3 Previous Work TIPS + TIPS 10 mol% HTf 2 CH 2 Cl 2, 0.1 M [2+2] HTf 2 TIPS H Tf 2 TIPS prepared independently H Si 3 Tf 2 H 3 Si Tf 2 Zhao, W.; Wang, Z.; Sun, J. Angew. Chem. Int. Ed. 2012, 51, 6209 Josh Wipf Group Page 3 of 11 4/21/2013
4 xetene Fragmentation? Josh Wipf Group Page 4 of 11 4/21/2013
5 eal Examples Ts AgSbF 6 (10%) DCE (0.25 M) 25 C, 99% Ts Ts H h! (254 nm) Et Me 3 MeC/H 2 89% BF 3 Et 2 Et 2, rt, 10 d 45% BF 3 H hee, J. U.; Krische, M. J. rg. Lett. 2005, 7, 2493 Arumugam, S.; Popik, V. V. J. Am. Chem. Soc. 2009, 131, Harding, C. E.; King, S. L. J. rg. Chem. 1992, 57, 883 Josh Wipf Group Page 5 of 11 4/21/2013
6 Ynolates X ' LDA X Li ' t-buli Li Li ' - Li' Li X X ' s- or t-buli or Li/naphtalene Li H Li Li - C Li Li TIPS-Tf TIPS Shindo, M. Tetrahedron, 2007, 63, 10 Shindo, M.; Mori, S. Synlett, 2008, 2231 Josh Wipf Group Page 6 of 11 4/21/2013
7 Ynol Ether Scope Me + TIPS BF 3 Et 2 2,4,6-collidine CH 2 Cl 2 (0.1 M) 0 C, 30 min Entry n-ct (CH 2 ) 3 c-pr t-bu (CH 2 ) 3 TIPS C 8 H 17 yield 91% 85% 77% 89% 84% 64% 62% 58% ptimized acetal, Lewis acid, additive Sterics not an issue Conjugation problematic H (unstable ynol ether) Josh Wipf Group Page 7 of 11 4/21/2013
8 Proposed Mechanism BF 3 collidine BF 3 ' TIPS ' ' LA LA ' ' BF 2 + F TIPS Josh Wipf Group Page 8 of 11 4/21/2013
9 Ketals: Selected Examples TIPS n ' BF 3 Et 2, 2,4,6-col n % 77% 8 CH 3 8 TBS Bz 3 -allyl -propargyl yield 75% 56% 52% 65% 63% H % 88% (1:1 E/Z) Bn Bn Bn 87% Bn Ac (E) 70% o eaction Josh Wipf Group Page 9 of 11 4/21/2013
10 Extensions Iterative ing Expansion: TIPS Ac BF 3 Et 2, 2,4,6-col 93% 1) H 2, Pd/C 2) DIBAL; Ac 2, py 68% Ac TIPS BF 3 Et 2, 2,4,6-col 65% TIPS TIPS Acyclic Systems: Ac n-c 5 H 11 TIPS BF 3 Et 2, 2,4,6-col 86% n-c 5 H 11 TIPS BF 3 Et 2, 2,4,6-col 83% (5.7:1 E/Z) H Josh Wipf Group Page 10 of 11 4/21/2013
11 Conclusion ew methodology for forming medium- and large-ring lactones Unprecedented ring expansion reaction manifold for oxetenes ormal reaction concentrations, no slow addition Iterative process possible to generate large rings from inexpensive material Must use substituted alkynes due to instability Potential problems with electronics of alkyne Limited use in complex systems to date. Josh Wipf Group Page 11 of 11 4/21/2013
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