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Recent Advances of Bismuth(III) Salts in Organic Chemistry: Application To

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Recent Advances of Bismuth(III) Salts in Organic Chemistry: Application To Mini-Reviews in Organic Chemistry, 2009, 6, 241-274 241 Recent Advances of Bismuth(III) Salts in Organic Chemistry: Application to the Syn- thesis of Aliphatics, Alicyclics, Aromatics, Amino Acids and Peptides, Terpenes and Steroids of Pharmaceutical Interest Jorge A.R. Salvador a,*, Rui M.A. Ppinto a and Samuel M. Silvestreb a Laboratório de Química Farmacêutica, Faculdade de Farmácia, Universidade de Coimbra, Polo das Ciências da Saúde, Azinhaga de Santa Comba, 3000-548, Coimbra b Centro de Investigação em Ciências da Saúde, Faculdade de Ciências da Saúde, Universidade da Beira Interior, Av. Infante D. Henrique, 6201-506 Covilhã, Portugal Abstract: In this review recent uses of the inexpensive and commercially available bismuth(III) salts in organic chemistry will be high- lighted. Their application to the development of new processes or synthetic routes that lead to compounds of pharmaceutical interest will be matter of discussion. It will focus on bismuth(III) salt-mediated reactions involving the preparation of non-heterocyclic compounds such as aliphatics and alicyclics, monocyclic and polycyclic aromatics, amino acids and peptides, terpenes and steroids. Keywords: Bismuth(III) salts, aliphatics, alicyclics, aromatics, amino acids, peptides, terpenes, steroids, pharmaceutical interest. 1. INTRODUCTION try point of view [4]. This review focuses on the use of bismuth(III) The increasing concern about the environment and the need for salts for the synthesis of the following groups of non-heterocyclic “green reagents” has placed bismuth and its compounds into focus compounds: aliphatics and alicyclics, monocyclic and polycyclic over the last decade. Despite the fact that bismuth is a heavy metal, aromatics, amino acids and peptides, terpenes and steroids, and has bismuth and bismuth(III) salts are considered safe, non-toxic and been organized according to the nature of the reaction products. appropriate “ecofriendly” reagents for green chemistry purposes When appropriate, examples of biological relevance will be pre- [1]. Moreover, bismuth has an electron configuration of sented as well as the final products of pharmaceutical interest in the [Xe]4f145d106s26p3, and due to the weak shielding of the 4f elec- course of synthetic routes. trons (Lanthanide contraction), bismuth(III) compounds exhibit Lewis acidity, which may be accentuated by strong withdrawing 2. ALIPHATIC AND ALICYCLIC COMPOUNDS groups such as triflate. Concerning the discrepancy related to the Allyl-bismuth(III) dihalides, generated by transmetallation of presentation of an uniform designation for the hydration number of allylstannanes with bismuth(III) halides, were found to be useful bismuth(III) triflate, this salt will be written as Bi(OTf)3·xH2O, intermediates for reactions with aldehydes. High levels of 1,5- following the discussion previously made by Gaspard-Iloughmane stereocontrol were observed from the reaction with 5-benzyloxy-4- and Le Roux [2a]. If many bismuth-promoted reactions can be ex- RCHO (3.0 eq.) OH Me OH Me BiI3 (1.0 eq.) OBn OBn Bu3Sn OBn R + R solvent, r.t., 30 min Me 1,5-anti-(E)-epimer 1,5-syn-(E)-epimer 51-92 % R = CH3CH=CH, (CH3)2CH, n-Pr, Ph, p-2ONC6H4 or p-OMeC6H4 ratio 1,5-anti-(E)/1,5-syn-(E) > 90:10 ca. 5 % of anti-(Z)-alkenol as by product Scheme 1. plained at the light of its Lewis acid character, recent works estab- methylpent-2-enyl(tributyl)stannane (up to a ratio of 93:3 in favor lished a role for the acid protons derived from the hydrolysis of of 1,5-anti-(E)-epimers), however in moderate to good yields. Sev- bismuth(III) salts, designated by “the hidden «Bi» behavior of bis- eral examples using aromatic and non-aromatic aldehydes were muth” [2a]. reported [5] (Scheme 1). Similar results can be achieved starting The use of the inexpensive and commercially available bis- from allylbromine derivatives using the BiI3/Zn system as an in situ muth(III) salts in organic chemistry [2] as well as in biological and generator of Bi(0) [6]. The reaction products of these reactions can medicinal chemistry [3] has been the subject of several reviews. In be seen as adequate intermediates for the synthesis of naturally this review recent applications of these reagents to organic synthe- occurring compounds bearing a 1,5-syn-dimethyl moiety (see dis- sis will be discussed. Special emphasis will be placed on the devel- cussion in [6, 7]). opment of new processes or synthetic routes using bismuth(III) salt- Due to their importance both as bioactive lead compounds [8] mediated reactions that lead to compounds of pharmaceutical inter- and as versatile building blocks [9], the synthesis of -enaminone est. Our intention has been to highlight the potential of bismuth- and -enamino esters has been an active field of research in organic promoted reactions for the construction and/or functionalization of chemistry. These compounds can be obtained by the direct conden- important molecular structures valuable from the medicinal chemis- sation of -dicarbonyl compounds with amines. The reaction can be performed in water [10] or tetrabutylammonium bromide (TBAB) [11] using bismuth(III) trifluoroacetate, Bi(TFA)3, as catalyst. The * Address correspondence to this author at the Laboratório de Química Farmacêutica, advantage of the Bi(TFA) /TBAB system is the fact that it can be Faculdade de Farmácia, Universidade de Coimbra, Polo das Ciências da Saúde, Azin- 3 haga de Santa Comba, 3000-548, Coimbra; Tel: +351 239488400; Fax: +351 recovered and reused. Both methods have been applied to the syn- 239827126; E-mail: [email protected] thesis of aliphatic (Scheme 2) and aromatic enaminones. 1570-193X/09 $55.00+.00 © 2009 Bentham Science Publishers Ltd. 242 Mini-Reviews in Organic Chemistry, 2009, Vol. 6, No. 4 Salvador et al. R O O R1 H 1 Bi(TFA)3 (0.05 eq.) NO N + H H Me R2 Me R2 H2O ------- r.t. ------ 5-180 min ----------------- 63-98 % TBAB ---- r.t. ------- immediately-15 min ---- 87-99 % R1 = n-Bu, H2NCH2CH2, HOCH2CH2 or CH3CH2CHCH3 R2 = OEt or Me Scheme 2. O R O BiCl3 (0.05 eq.) 1 R1 R2 + R3COCl Cl R O CH2CH2, r.t. 3 R R3 = Me > 95 % 2 R1 = H or Me i-Pr R2 = H or Me t-Bu AcO(CH3)CH CH2 Scheme 3. O O 8 COOMe BiBr3 (0.3 eq.) 8 COOMe TBSO CH3CN/H2O, r.t. HO 62 % OTBS OH lipase (PPL) H2O/THF NaCl, CaCl2 O 8 COOH HO OH 8-epi-PGE2 Scheme 4. The O-acylative cleavage of cyclic ethers has been reported in Nicolaou and co-workers reported the use of Bi(OTf)3·xH2O, the presence of bismuth(III) salts. The cleavage of tetrahydrofuran among other catalysts, in the annulation reaction between simple and its 2-methyl and 2,5-dimethyl derivatives with aliphatic and cyclic ketones and ,-unsaturated aldehydes to afford polyfunc- alicyclic acyl halides, catalyzed by Bi(III) halides, in CH2Cl2 at 20 tional molecules with bridged medium rings (Scheme 5). These ºC, resulted in the formation of aliphatic and alicyclic halo- bicyclic hydroxy diketones constitute the core of important natu- acyloxyester derivatives, respectively, in very high yields (Scheme rally occurring compounds, such as hyperforin a metabolite isolated 3) [12, 13]. More recently, Bi(III) salts, including Bi(NO3)3·5H2O, from Hypericum perforatum (St. John’s wort), famous for its anti- Bi(OTf)3·xH2O and BiCl3 were reported as catalyst (5-10 mol %) depressant properties. Moreover, these bicyclic hydroxy diketones for the cleavage of cyclic and acyclic ethers using aromatic and can be further functionalized by oxidation and subsequent ring aliphatic acyl chlorides, under solvent-free conditions [14]. fragmentation to large-size ring containing derivatives, which are The use of BiBr has been reported for the mild cleavage of also of considerable interest (e.g. perforatumone, also found in 3 Hypericum perforatum) [18]. silyl protective groups during the total synthesis of E1 and E2 iso- prostanes [15]. This modification of Bajwa et al. procedure [16], The use of Bi(OTf)3·xH2O has been reported for the preparation which uses a slightly higher amount of BiBr3 (30 mol %) in of polysubstituted six-membered carbocycles. Although better re- CH3CN/H2O at room temperature, allowed the selective cleavage of sults were accomplished by the use of Sn(IV) salts, the cycloi- the TBS protecting group avoiding epimerization to the thermody- someration of 1,6-diene diethyl diprenylmalonate afforded the cor- namically more stable trans-isomer (Scheme 4). E1 and E2 iso- responding gem-dimethyl cyclohexene product in 23 % yield, after prostanes have been identified in vivo, and recent studies estab- 7 h, at 83 ºC using 5 mol % of the bismuth(III) catalyst (Scheme 6) lished their role in important biological processes [17]. [19]. Recent Advances of Bismuth(III) Salts in Organic Chemistry Mini-Reviews in Organic Chemistry, 2009, Vol. 6, No. 4 243 O CHO O HO Bi(OTf)3·xH2O (0.3 eq.) (n) ˚ CH2Cl2, -78 to 25 C, 6-24 h (n) 29-58 % O n = 1, 2 or 3 Oxidation O O O (n) O HO O Fragmentation O O (n) Hyperforin, metabolite isolated from O O Hypericum perforatum HO Scheme 5. O EtO2C Bi(OTf) ·xH O (0.05 eq.) EtO C 3 2 2 EtO2C ˚ EtO2C ClCH2CH2Cl, 83 C, 7 h Conversion = 31 % 23 % Scheme 6. 3. MONOCYCLIC AND POLYCYCLIC AROMATIC COM- have been reported for the synthesis of both 1,1-diaryalkanes and POUNDS 1,1-diarylalkenes. Aromatic rings constitute quite rigid, flat, relatively lipophilic Le Rouzo et al. reported the highly para-regioselective synthe- moieties with considerable electron density. This electron density sis of 4-cumylphenol in 78 % yield from the Friedel-Crafts alkyla- can be modulated by substituents attached to the aromatic ring with tion of phenol with -methylstyrene in the presence of electron donating or withdrawing character.
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