Cafestol to Tricalysiolide B and Oxidized Analogues: Biosynthetic and Derivatization Studies Using Non-heme Iron Catalyst Fe(PDP)

Marinus A. Bigi; Peng Liu; Lufeng Zou; K. N. Houk; M. Christina White

doi:10.1055/s-0032-1317708

Synlett, Inhaltsverzeichnis

Synlett 2012; 23(19): 2768-2772
DOI: 10.1055/s-0032-1317708

cluster

Cafestol to Tricalysiolide B and Oxidized Analogues: Biosynthetic and Derivatization Studies Using Non-heme Iron Catalyst Fe(PDP)

Marinus A. Bigi

^aRoger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, IL 61801, USA Fax: +1(217)2445943 eMail: white@scs.uiuc.edu

,

Peng Liu

^bDepartment of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, USA Fax: +(310)2061843 eMail: houk@chem.ucla.edu

,

Lufeng Zou

^bDepartment of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, USA Fax: +(310)2061843 eMail: houk@chem.ucla.edu

,

K. N. Houk*

^bDepartment of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, USA Fax: +(310)2061843 eMail: houk@chem.ucla.edu

,

M. Christina White*

^aRoger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, IL 61801, USA Fax: +1(217)2445943 eMail: white@scs.uiuc.edu

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

The tricalysiolides are a recently isolated class of diterpene natural products featuring the carbon backbone of the well-known coffee extract, cafestol. Herein we validate the use of our non-heme iron complex, Fe(PDP), as an oxidative tailoring enzyme mimic to test the proposal that this class of natural products derives from cafestol via cytochrome P-450-mediated furan oxidation. Thereafter, as predicted by computational analysis, C–H oxidation derivatization studies provided a novel 2° alcohol product as a single diastereomer.

Key words

C–H oxidation - functionalization - aliphatic - non-heme iron - natural product diversification - biosynthesis - cafestol

Volltext

Referenzen

References and Notes
1 Denisov IG, Makris TM, Sligar SG, Schlichting I. Chem. Rev. 2005; 105: 2253

2a Bruijnincx PC. A, van Koten G, Gebbink RJ. M. K. Chem. Soc. Rev. 2008; 37: 2716
2b Merkx M, Kopp DA, Sazinsky MH, Blazyk JL, Müller J, Lippard SJ. Angew. Chem. Int. Ed. 2001; 40: 2782
2c Neumann CS, Fujimori DG, Walsh CT. Chemistry & Biology 2008; 15: 99
2d Costas M, Mehn MP, Jensen MP, Que Jr. L. Chem. Rev. 2004; 104: 939

3a Okuno T, Ito S, Ohba S, Nishida YJ. Chem. Soc., dalton Trans. 1997; 3547
3b Kim C, Chen K, Kim J, Que Jr L. J. Am. Chem. Soc. 1997; 119: 5964
3c Wu X, Seo MS, Davis KM, Lee Y.-M, Chen J, Cho K.-B, Pushkar YN, Nam W. J. Am. Chem. Soc. 2011; 133: 20088
3d Bigi JP, Harman WH, Lassalle-Kaiser B, Robles DM, Stich TA, Yano J, Britt RD, Chang CJ. J. Am. Chem. Soc. 2012; 134: 1536
3e Groves JT, Neumann R. J. Org. Chem. 1988; 53: 3891
3f Breslow R, Huang Y, Zhang X, Yang J. Proc. Natl. Acad. Sci. U.S.A. 1997; 94: 11156
3g Das S, Incarvito CD, Crabtree RH, Brudvig GW. Science 2006; 312: 1941

4 Chen MS, White MC. Science 2007; 318: 783
5 Chen MS, White MC. Science 2010; 327: 566
6 White MC, Doyle AG, Jacobsen EN. J. Am. Chem. Soc. 2001; 123: 7194
7 Chen K, Que LJr. J. Am. Chem. Soc. 2001; 123: 6327
8 Bigi MA, Reed SA, White MC. Nat. Chem. 2011; 3: 218
9 Pochapsky TC, Kazanis S, Dang M. Antioxid. Redox Signaling 2010; 13: 1273
10 Gross G, Jaccaud E, Huggett AC. Food Chem. Toxicol. 1997; 35: 547
11 Nishimura K, Hitotsuyanagi Y, Sugeta N, Sakakura K, Fujita K, Fukaya H, Aoyagi Y, Hasuda T, Kinoshita T, He D.-H, Otsuka H, Takeda Y, Takeya K. Tetrahedron 2006; 62: 1512
12 Nishimura K, Hitotsuyanagi Y, Sakakura K, Fujita K, Tachihara S, Fukaya H, Aoyagi Y, Hasuda T, Kinoshita T, Takeya K. Tetrahedron 2007; 63: 4558
13 Bigi MA, Reed SA, White MC. J. Am. Chem. Soc. 2012; 134: 9721
14 White MC. Science 2012; 335: 807

For examples in aliphatic C–H chlorinations and fluorinations with Mn porphyrins, see:

15a Liu W, Groves JT. J. Am. Chem. Soc. 2010; 132: 12847
15b Liu W, Huang X, Cheng M.-J, Nielsen RJ, Goddard WA. III, Groves JT. Science 2012; 337: 1322

For an example with allylic C–H aminations using an Fe-phthalocyanine catalyst, see:

15c Paradine SM, White MC. J. Am. Chem. Soc. 2012; 134: 2036

16 Kurzrock T, Speer K. Food Rev. Int. 2001; 17: 433
17 Cavin C, Holzhaeuser D, Scharf G, Constable A, Huber WW, Schilter B. Food Chem. Toxicol. 2002; 40: 1155
18 Trinh K, Andrews L, Krause J, Hanak T, Lee D, Gelb M, Pallanck L. J. Neurosci. 2010; 30: 5525
19 Guengerich FP. Arch. Biochem. Biophys. 2003; 409: 59
20 Bertholet, R.; US 4692534, 1987.
21 No differences in reactivity or selectivity have been observed running Fe(PDP) oxidations under N₂ or Ar atmosphere vs. running the reaction open to air. This along with the stereoretentive nature of oxidation suggests the reaction does not proceed via hydroxyl radicals or a long-lived carbon radical intermediate.
22 Bal BS, Childers WE. Jr, Pinnick HW. Tetrahedron 1981; 37: 2091
23 vanCruchten ST. J, deHaan LH. J, Mulder PP. J, Kunne C, Boekschoten MV, Katan MB, Aarts JM. M. J. G, Witkamp RF. J. Nutr. Biochem. 2010; 21: 757
24 MacroModel, version 9.9; Schrödinger LLC: New York, 2011.
25 Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA. Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Keith T, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ. Gaussian 09, Revision B.01 2009;
26 NPA charges were calculated using B3LYP/6-311++G(d,p). Mulliken charges were calculated using B3LYP/6-31G(d) (see Supporting Information) and provided an analogous trend to the NPA charges. Mulliken charges are an excellent alternative when minimizing computation power and time are a consideration.��
27 These steric and electronic property analyses were all based on calculations of the reactant molecule. Density functional theory (DFT) calculations of transition-state structures and selectivities are under way in our labs to verify these selectivity rules.

Zusatzmaterial

Supporting Information