A Concise Synthesis of ( )- Aplyviolene Facilitated by a Stragetegic Ter<ary Radical Conjugate Addi<on

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1 A Concise Synthesis of ( )- Aplyviolene Facilitated by a Stragetegic Ter<ary Radical Conjugate Addi<on Schnermann, M. J.; verman, L. E. Angew. Chem. Int. Ed. 2012, 51, February, 13 th 2014 Presented by Julien

2 Introduc<on Isolated from sponges and nudibranchs (1986) (Class of rearranged spongian diterpene) 6- acetoxy- 2,7- dioxabicyclo[3.2.1.]octan- 3- one ring Cis- perhydroazulene fragment (bicyclo[5.3.0]decane) 7 stereogenic centers Aplyviolene 1 Ac Second total synthesis of Aplyviolene azulene ambley, T. W.; Poiner, A.; Taylor, W. C. Tetrahedron Le , 27, Molinski, T. F.; Faulkner, D. J.; e, C..; Van Duyne, G. D.; Clardy, J. J. rg. Chem. 1986, 51,

3 C 2 TBS 9 Br First genera<on Synthesis 2 11 Steps 11 LDA, MPA TF, rt then 9, 78 C (81%) 2 C TBS 12 Br 2 CuCLi 2 TBSCl, MPA 78 C (86%) 2 C TBS 13 TBS ab 4 CeCl 3 (71%) 2 C TBS 14 TBS 1. amds CS 2, I (83%) 2. Bu 3 Sn AIB (85%) 2 C TBS 8 TBS Schnermann, M. J.; verman, L. E. J. Am. Chem. Soc. 2011, 133,

4 First genera<on synthesis 2 C TBS TBS 9 Steps Ac 8 Aplyviolene 1 Schnermann, M. J.; verman, L. E. J. Am. Chem. Soc. 2011, 133,

5 Second genera<on synthesis Retrosynthesis Ac 2 C TBS TBS Aplyviolene C TBS 28 Cl + 27 X 19 (+)-fenchone Schnermann, M. J.; verman, L. E. Angew. Chem. Int. Ed. 2012, 51,

6 Br Ph 3 P A Second genera<on Synthesis 19 (+)-fenchone 2 Cl (1.75 eq) aac (2 eq) Et, reflux, 36 h 2 S 4 (4M) reflux, 8h (83% from 19) C 20 2:1 Δ 1,2 :Δ 1,5 1. DIBAL- (1.2 eq) DCM, 78 C, 1h 2. A (2 eq), n-buli (4 eq) TMSCl (2 eq), TF, 0 C, 20 min then aldehyde from step 1 78 C, 1 h 3. 2 Cl, rt, 18 h (55 % from 20) 21 Schnermann, M. J.; verman, L. E. Angew. Chem. Int. Ed. 2012, 51,

7 Second genera<on Synthesis 1. I 2 (1.05 eq), PPh 3 (1.05 eq) Imidazole (1.1 eq), benzene 18 h, rt (94%) Ag 2 (1.5 eq) 18 h, rt (67%) PhC (3 eq), Et 3 (0.5 eq) toluene, 18 h, 90 C Ts (0.1 eq) 2. 2, 10% Pd/C (5 wt%) Raney-i (5 wt%), B() 3 (3 eq) / 2 (5:1), 36 h, rt (67% from 22) 23 5 h, 100 C (91%) 24 Schnermann, M. J.; verman, L. E. Angew. Chem. Int. Ed. 2012, 51,

8 Second genera<on Synthesis MgBr (5 eq) CuC (2.5 eq) 1. TMSC 2 Li (5 eq), pentane, 78 C 2. 3, DCM, 78 C then PPh 3 (1.5 eq), F Pyridine, 1h, 0 C 24 TF/MPA (5:1) 7 h, 0 C (77%) acl 2 (3 eq), a 2 P 4 (1 eq) 2-methyl-2-butene (3 eq) acetone/ 2 (30:1), rt, 1 h (74% from 25) C 2 -(hydroxy)phtalimide (1.7 eq) DCC (1.5 eq), DMAP (0.05 eq) Phth 26 TF, 18 h, rt (84%) 27 Schnermann, M. J.; verman, L. E. Angew. Chem. Int. Ed. 2012, 51,

9 Et 2 C 29 C 2 Et Second genera<on Synthesis 27 Phth + 2 C TBS 28 (1.5 eq) Cl 29 (1.5 eq) [Ru(bpy) 3 ](BF 4 ) 2 (0.01 eq) DCM Blue LEDS, 2.5 h, rt (61%) 2 C TBS Cl 30 single diastereoisomere Schnermann, M. J.; verman, L. E. Angew. Chem. Int. Ed. 2012, 51,

10 Second genera<on Synthesis 2 C TBS Cl 30 single diastereoisomere 2 CuCLi (2.0 eq) TBSCl (5 eq) Et 2 /TF/MPA (4:2:1) 1h, 20 C (76%) 2 C TBS 8 TBS 1. TiCl 4, Zn C 2 Br 2 (97%) 2. oxalic acid (57%) TBS 13 TBS 1. s 4 M 2. Pb(Ac) 4 (81% from 13) TBS 14 C 2 TBAF TF, 0 C (69%) 2 C 15 Schnermann, M. J.; verman, L. E. J. Am. Chem. Soc. 2011, 133, Schnermann, M. J.; verman, L. E. Angew. Chem. Int. Ed. 2012, 51,

11 End of the Synthesis 2 C 2 C 15 DAST DCM 78 C 16 F 1. a 2. SnCl 2, DMF (76% from 15) 17 m-cpba (61%) Aplyviolene 1 Ac Schnermann, M. J.; verman, L. E. J. Am. Chem. Soc. 2011, 133, Schnermann, M. J.; verman, L. E. Angew. Chem. Int. Ed. 2012, 51,

12 2 Conclusion Both synthesis by verman (2011 and 2012) 2011 : overall Yield = 0.7% (25 steps) 2012: overall Yield = 0.6% (26 steps) 1 st genera<on: Key step : Michael addi<on 2 nd genera<on: Key step : Photoredox catalysis 19 (+)-fenchone 12 Schnermann, M. J.; Un<edt,. L.; Jiménez- sés, G.; ouk, K..; verman, L. E. Angew. Chem. Int. Ed. 2012, 51,

13 Thank you for your aien<on

14 Synthesis of 9 Cl C 3 CCC 3 (1 eq) CSA (0.1 eq) C(C 3 ) 3 (2.1 eq), reflux, 2h Cl t BuK (2 eq) TF, reflux, 2h 3 DCM/ (1:1, v/v) 78 C then DMS (2 eq) 78 C rt (56% over three steps) Dixon, D. J.; Ley, S. V.; Polara, A.; Sheppard, T. rg. Le , 3, Ley, S. V.; Baeschlin, D. K.; Dixon, D. J.; Foster, A. C.; Ince, S. J.; Priepke,.; Reynolds, D. J. Chem. Rev. 2001, 101,

15 Synthesis of 9 TMS Et TBAT TF, rt TMS Ac LiAc, DMF 2 (63%) TFA then 2 S 4 K 2 C 3 (88%) C 2 1. TBSCl, DMAP (83%) 2. Br 2 (84%) C 2 TBS 9 Br Schnermann, M. J.; Beaudry, C. M.; Genung,. E.; Canham, S. M.; Un<edt,. L.; Karanikolas, B. D. W.; Süierlin, 15 C.; verman, L. E. J. Am. Chem. Soc. 2011, 133,

16 Synthesis of s 4 (cat.), ai 4 Et 2, 2, 0 C 2. PhS, BF 3 Et 2 DCM, 78 C 2 (89%) 3 Ph Ph (0.2 eq) B B 3 TF (0.6 eq) TF, 78 C 4a (49%, 79% ee) + 4b (44%, 94% ee) Lebsack, A. D.; verman, L. E.; Valentekovich, R. J. J. Am. Chem. Soc. 2001, 123,

17 S S BF 4 DMTSF Synthesis of 11 4b 1. (E)-C=CLi TF/Et 2, 100 C 2. TMS-imidazole, 120 C (92%) TMS 5 DMTSF, DCM 45 C (80%) 6 (5:1 ; β:α) 1. TMSC 2 Li, 78 C pentane/tf 1. m-cpba, DCM 78 C 0 C (78%) 2. F Pyr, C, rt (84%) 7 2. MoP, LDA, TF 78 C (80 C) 11 Lebsack, A. D.; verman, L. E.; Valentekovich, R. J. J. Am. Chem. Soc. 2001, 123,

18 chanism Ph Ph Ph C 2 Ph 2 22 Ph Pd/C, 2 Raney i B() 3 23 Ph Ph Mukaiyama, T.; oshino, T. J. Am. Chem. Soc 1960, 82, Curran, D. P. J. Am. Chem. Soc. 1983, 105,

19 chanism [R 3 ] + R 3 *[Ru II (bpy) 3 ] 2+ hυ [Ru II (bpy) 3 ] + [Ru II (bpy) 3 ] 2+ Et 2 C C 2 Et o reac<on with : - ter<ary chloride or bromide - Barton ester kada, K.; kamoto, K.; Morita,.; kubo, K.; da, M. J. Am. Chem. Soc. 1991, 113, Andrews, R. S.; Becker, J. J.; Gagné, M. R. Angew. Chem. Int. Ed. 2010, 49, Andrews, R. S.; Becker, J. J.; Gagné, M. R. rg. Le , 13,

20 First genera<on synthesis Retrosynthesis Ac 2 C TBS TBS Aplyviolene C TBS 12 Br 11 + C 2 TBS 9 Br Schnermann, M. J.; verman, L. E. J. Am. Chem. Soc. 2011, 133,

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