Application of Two Direct C(sp 3 )-H Functionalizations for the Total Synthesis of (+)-Lactacystin
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1 Application of Two Direct C(sp 3 )- Functionalizations for the Total Synthesis of (+)-Lactacystin two stereoselective C(sp 3 )- functionalisations 2 C S Ac (S)-pyroglutaminol (+)-lactacystin S. Yoshioka, M. agatomo, M. Inoue rg. Lett., 2015, 17 (1), pp Graduate School of armaceutical Science The University of Tokyo, ongo, Bungyo-ku, Tokyo DI: /ol503291s Samuel Rieder, 8. Jan. 2015
2 istory Previous Studies and Synthesis - Isolated from Streptomyces sp. M-6519 by mura in Proteasom Inhibitor, Cancer Treatment - Significant attention as synthetic target: - Total Synthesis (13) - Corey (1992), Smith (1993), Russel (1994), gawa (1995), Corey (1998), Corey (1998), Masse (1999), Plamondon (1999), atakeyama (2004), Shibasaki (2006), Jacobsen (2006), Prodger (2008), Silverman (2011) - Formal Total Synthesis (12) - Jun (1998), Youn (1998), hfune (2000), arling (2005), Bowen (2005), Jung (2007), Kobayashi (2007), Langlois (2007), Rescourio (2008), ayes (2010), ayes (2013), Chandrasekhar (2014) 2
3 Development Comparison to first TS - Corey s approach (1992) t-bu C 2 13 steps 6% overall yield S Ac (+)-lactacystin - This approach (2014) 20 steps 1.4% overall yield S Ac (S)-pyroglutaminol (+)-lactacystin E. J. Corey, G. A. Reichard, J. Am. Chem. Soc. 1992, 114,
4 Retrosynthetic Pathway Starting from (S)-pyroglutaminol (6) Ac S R 1 2 C 1 2 R2 hν C(sp 3 ) acylation R 1 R 2 3 R 1 R 2 hν C(sp 3 ) alkynylation R 1 R 2 TMS Direct transformation of C(sp 3 ) bonds to C(sp 3 ) C bonds eliminates the preactivation à Permits design of simpler synthetic schemes 4
5 Synthesis Preliminary Studies, Developments - Intermolecular C(sp 3 ) functionalization hν (g lamp) BP Ts TMS TMS - Selectivity (α- ydrogen à α- ydrogen à aliphatic ydrogen) - Intramolecular C(sp 3 ) functionalization hν (g lamp) BP 5 I 6 - orrish-yang cyclization followed by oxidative ring opening T. oshikawa, S. Kamijo, M. Inoue, rg. Biomol. Chem. 2013, 11, S. Kamijo, T. oshikawa, M. Inoue, Tetrahedron Lett. 2010, 51, 872 5
6 Synthesis Exploring the Selectivity Towards Alkynylation Product C() 2 pts 2, reflux, 68% benzaldehyde p-ts 2, reflux, 73% LDA, I TF, 78 C, 60% Ts TMS BP, hν (g lamp) t-bu, 1~2 d 62% (dr = 4:1) Ts TMS BP, hν (g lamp) t-bu, 1~2 d Side-reaction at benzylic position à thylation Moderate stereoselectivity à thylation TMS TMS Ts TMS BP, hν (g lamp) t-bu, 1~2 d K 2 C 3, 0 C 12% (2 steps) R R = TMS R = K 2 C 3, 0 C 54% (2 steps) 6
7 Synthesis Second C(sp 3 ) Functionalization LMDS Tf TF, 78 C 99% Ru 2 2 (cat.) ai 4 CCl 4 /C/ 2, 0 C 70% 24 W blue LED, 18 h Pb(Ac) 4 a 2 C 3, 0 C 66% (2 steps) 2 C - orrish-yang cyclization not working with g lamp, photoexcitaion of ketol à LED longer wavelength - Epimerization observed without a 2 C 3 Carlsen, P.. J.; Katsuki, T.; Martin, V. S.; Sharpless, K. B. J. rg. Chem. 1981, 46,
8 Synthesis Construction of (+)-Lactacystin I 2 C Cp 2 Ti 2 TF, 85 C 2 C TFA TF/ 2, 60 C 68% (2 steps) C 2 1. Ac 2, DMAP py 2. Boc 2, DMAP Et 3, C 2 Cl , Pd/C EtAc 63% (3 steps) Ac Boc C 2 1. LMDS SeBr TF, 78 C , ac 3 TF/EtAc, 0 C 73% (2 steps) Ac Boc C 2 Et 2 Zn Et 2 2 SiLi TF, 78 C Boc m-cpba, KF 2 DMF Boc then methyl salicylate R Ac C 2 i-pr 66% (2 steps) Ac C 2 i-pr R = Si 2 (Et 2 ) R = Si 2 Tamao, K.; Kawauchi, A.; Ito, Y. J. Am. Chem. Soc. 1992, 114, 3989 Crump, R. A.. C.; Fleming, I.; Urch, C. J. J. Chem. Soc., Perkin Trans , 701 8
9 Synthesis Construction of (+)-Lactacystin II Boc 1. TFA C 2 Cl 2 BP-Cl, Et 3 Ac C 2 i-pr 2. aq a, 0 C C i-pr C 2 Cl 2 52% (2 steps) -acetyl-l-cysteine Et 3, C 2 Cl 2 87% S Ac (+)-lactacystin P Cl BP-Cl 9
10 Conclusion - ovel route to (+)-lactacystin from (S)-pyroglutaminol - Reasonable application of intermolecular C alkynylation and intramolecular C acylation - igh applicability of the two C(sp 3 ) functionalizations - igh predictability of their chemoselectivities (α- à α- à aliphatic ) - Further applications are under investigation Thank you for your attention 10
11 Supplementary Information Intermolecular C(sp 3 ) Functionalization T. oshikawa, S. Kamijo, M. Inoue, rg. Biomol. Chem. 2013, 11,
12 Supplementary Information Explanation for Stereochemical utcome of Alkynylation S. Yoshioka, M. agatomo, M. Inoue, rg. Lett. 2015, 17,
13 Supplementary Information Protonation of Fleming-Tamao xidation Enolate 13
14 Supplementary Information Biosynthesis A. akagawa, M. Kainosho and S. Õmura, Pure Appl. Chem. 1994, 66(10-11),
15 Supplementary Information orrish-yang Cyclization + hν singlet orrish type II 1 (nπ)* or 3 (nπ)* triplet orrish-yang S. Chiba,. Chen, rg. Biomol. Chem., 2014, 12,
Radical Reactions. Radical Stability!!! bond dissociation energies X Y X + Y. bond BDE (kcal/mol) bond BDE (kcal/mol) CH 3 CH 3 CH 2 95 O H R 2 C H
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