Total Synthesis of the Proposed Structure of Briarellin J
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1 Total Synthesis of the Proposed Structure of Briarellin J Michael T. Crimmins, Mark C. Mans, and Abimael D. Rodríguez. rg. Lett. 2010, ASAP Ac Ac originally proposed structure revised structure Eric E. Buck Current Literature ctober 23, 2010 ERic Wipf Group Page 1 of 16 12/5/2010
2 Isolation and Background" Briarellin J was isolated from the gorgonian octocoral Briareum polyanthes located of the south west coast of Puerto Rico. The briarellins, asbestinins, eunicellins, and sarcodyctins are structural subclasses of cembranoid diterpenes. C 3 7 C This class of diterpenes is thought to play a roll in predation deterrence Recently, the briarellin class of compounds has shown inhibition of Plasmodium falciparum, a parasite responsilbe for malaria. Briarellin J showed very little activity. Briarellin D hydroperoxide LC 50 = 9 µg/ml Rodríguez, A. D.; Cóbar,. M. Tetrahedron. 1995, 51, spina, C. A.; Rodríguez, A. D.; rtega-barria, E.; Capson, T. L. J. Nat. Prod. 2003, 66, ERic Wipf Group Page 2 of 16 12/5/2010
3 Proposed biosynthesis" cyclization cembrane cyclization eunicellins briarellins 1,2-methyl shift sarcodycytins asbestinins Stierle, D. B.; Carté, Faulkner, D. J.; Tagle, B.; Clardy, J. J. Am. Chem. Soc. 1980, 102, ERic Wipf Group Page 3 of 16 12/5/2010
4 The briarellin family" Ac briarellin E 11-acetoxy-4-deoxyasbestinin (synthesis by Crimmins, 2005) C 2 C 7 15 (synthesis by verman, 2003) C 3 7 C 2 Ac briarellin D (proposed) briarellin J originally proposed structure 9 19 The briarellin A-D and J-P have been assigned different C11 configurations than briarellin E-I The asbestinin family all share the same relative stereochemistry. The structure of briarellin J was proposed based on previously reported structural assignments of briarellin D and A The C11 configuration was based on the absence of an ne correlation between C11 and 14. bserved ne: C11 : 9, 10, 19 Ac : 1, 19 Not observed ne: C11 : 14 Ac : 14 ERic Wipf Group Page 4 of 16 12/5/2010
5 vermanʼs synthesis of Briarellins E and F" TIPS 3:1 + TBDPS C 1) p-ts 2, MgS 4, DCM -78 o C to -20 o C 0.1 equiv SnCl 4, DCM -78 o C to rt C TMS TMS 84% over 2 steps TIPS I C C 2 CC 7 15 CrCl 2 -NiCl 2 (100:1) DMS- 2 S (100:1) 79% C 2 C 7 15 briarellin E 28 steps *, 0.7% yield Corminboeuf,.; verman, L. E.; Pennington, L. D. J. Am. Chem. Soc. 2003, 125, Corminboeuf,.; verman, L. E.; Pennington, L. D. J. rg. Chem. 2009, 74, ERic Wipf Group Page 5 of 16 12/5/2010
6 Crimminsʼs synthesis of the Eunicelin, phirin B" Bn 3 SI, n-buli, TF, 99% PMBCl, Na Bn PMB g(ac) 2, 2 ; PdCl 2, LiCl, CuCl 2, 2, 2 89% Bn PMB 1) MgBr, TF, 94% Bn PMB 1), Cl, 65 o C, 85% 2) BrC 2 C 2, TF, DMF, 98% 2) BnBr, 93% Bn 3) 3 CCCl; A, 89% i-pr N Li N i-pr Bn A Bn Crimmins, M. T.; Brown, B.. J. Am. Chem. Soc. 2004, 126, Crimmins, M. T.; Brown, B..; Plake,. R. J. Am. Chem. Soc. 2006, 128, ERic Wipf Group Page 6 of 16 12/5/2010
7 Crimminsʼs synthesis of the Eunicelin, phirin B" i-pr i-pr Bn N NaMDS, 93% I Bn N LiB 4, 92% Bn Bn Bn A) Grubbs 2, DCM, 40 o C B) Grubbs 2, C 6 6, 80 o C + dimer Bn Bn Bn A) 75% 3:1 b) 89% >15:1 Crimmins, M. T.; Brown, B.. J. Am. Chem. Soc. 2004, 126, Crimmins, M. T.; Brown, B..; Plake,. R. J. Am. Chem. Soc. 2006, 128, ERic Wipf Group Page 7 of 16 12/5/2010
8 Crimminsʼs synthesis of the Eunicellin, phirin B" C Ph 3 P=CC 2 Bn + Z,E Bn Bn 2 C TES 2 C TES 2h, rt Bn C 2 TES Ac Ac Ac The Z,E isomer can be recycled by irradiation in the presence of PhSSPh phirin B 28 steps, 7.7% overall yield Crimmins, M. T.; Brown, B.. J. Am. Chem. Soc. 2004, 126, Crimmins, M. T.; Brown, B..; Plake,. R. J. Am. Chem. Soc. 2006, 128, ERic Wipf Group Page 8 of 16 12/5/2010
9 Crimminsʼs 11-acetoxy-4-deoxyasbestinin D" Bn 2 C TES C TBS 100 o C toluene, 80% TBS TBS Ac Established absolute configuration of the asbestinin family of diterpenes. Crimmins, M. T.; Ellis, J. M. J. Am. Chem. Soc. 2005, 127, Crimmins, M. T.; Ellis, J. M. J. rg. Chem. 2008, 73, linear steps 11-acetoxy-4-deoxyasbestinin ERic Wipf Group Page 9 of 16 12/5/2010
10 Title paper: Key Diels-Alder cycloaddition" 1) Swern [] 2 C TBS TBS 2) 2 C PPh 3 Cl DBU, CN, reflux TBS TBS 1) DIBAL- 2) Mn 2 3) Ph 3 P=C 2, 75% 4) N 4 F, 70% TBS 75% 1) TPAP, NM 2) PPh 3 toluene, reflux 62% TBS TBS Crimmins, M. T.; Mans, M. C.; Rodríguez, A. D. rg. Lett. 2010, ASAP ERic Wipf Group Page 10 of 16 12/5/2010
11 Title paper: Revision of absolute stereochemistry" TBS 1) Ph 3 P=C 2 2) F 3) DMP [] 79% Li 99% ne ne Ac Ac X-ray structure of the diol verifies stereochemistry 1) 9-BBN; NaB 3 2) DMP [] 71% Crimmins, M. T.; Mans, M. C.; Rodríguez, A. D. rg. Lett. 2010, ASAP p-ts 64% briarellin J originally proposed structure 15 linear steps from previously prepared oxonene The 1 and 13 C NMR spectra did not match the natural sample. ERic Wipf Group Page 11 of 16 12/5/2010
12 riginal structure" ERic Wipf Group Page 12 of 16 12/5/2010
13 Revised Structure" ERic Wipf Group Page 13 of 16 12/5/2010
14 Summary" Ac originally proposed structure Provided a rational that fits the observed ne correlations, verman s synthesis, and originally proposed biosynthesis. The Biosynthesis of this family has not been confirmed. Crimmins has determined the absolute configuration of several related diterpenes. Each family of diterpenes was generated through a similar exo-selective Diels-Alder cycloaddition Ac revised structure ERic Wipf Group Page 14 of 16 12/5/2010
15 ERic Wipf Group Page 15 of 16 12/5/2010
16 riginal characterization" Ac briarellin J originally proposed structure bserved ne: C11 : 9, 10, 19 Ac : 1, 19 Not observed ne: C11 : 14 Ac : C NMR shifts δ and 85.4 characteristic of seven-membered lactone ring. 13 C NMR shifts δ 91.9 and 80.6 which correlate by MQC to two oxymethine protons identify the typical TF ring. briarellin E C 2 C 7 15 (synthesis by verman, 2003) ERic Wipf Group Page 16 of 16 12/5/2010
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