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Reactivity Features of Cyclododecanone

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Reactivity Features of Cyclododecanone Reviews and Accounts ARKIVOC 2011 (i) 429-495 Reactivity features of cyclododecanone Hanafi H. Zoorob, Mohamed S. Elsherbini, and Wafaa S. Hamama* Chemistry Department, Faculty of Science, Mansoura University, El-Gomhoria Street, 35516 Mansoura, Egypt E-mail: [email protected] Abstract Cyclododecanone is a highly important synthetic intermediate for macrocyclic systems. This review is the sole and comprehensive one that covers the different aspects of cyclododecanone chemistry over the period from 1950 to 2010. Keywords: Cyclododecanone, muscone, fragrances, macrocylic ketones, ring enlargement and heterocycles Table of Contents 1. Introduction 2. Synthesis of Cyclododecanone 3. Chemistry of Cyclododecanone 3.1. Halogenation 3.2. Oxidation 3.3. Alkylation 3.4. Mannich reaction 3.5. Ring enlargement 3.5.1. Macrocyclic ketones and esters 3.5.2. Macrocyclic lactames and lactones 3.5.3. Macrocyclic Acetylenes 3.6. Ring contraction 3.7. Construction of spiro and fused heterocyclic systems 3.7.1. Spiro heterocyclic systems 3.7.2. Fused heterocyclic systems 3.8. Photochemistry 3.9. Miscellaneous reactions 4. Conformational Characteristics of Cyclododecanone 5. Conclusion Page 429 ©ARKAT-USA, Inc. Reviews and Accounts ARKIVOC 2011 (i) 429-495 6. Appendix: Abbreviations and Acronyms 7. References 1. Introduction Cyclododecanone 1 is a commercially available ketone, and important synthetic intermediate in the synthesis of natural products containing macrocyclic ring systems such as the anticancer rosphellin 2,1 the potent microglial activation modulators tocopherol fatty alcohols (TFAs) 3,2 cytotoxic sponge alkaloids motuporamine A 4, motuporamine B 5,3 ingenes 6 and 7,4,5 (Scheme 1). N RO O H3CO (CH2)n O O OH NH R=H,Me,Ac Cl n=11to15 Cyclododecanone roseophilin TFAs 1 23 H N N N H2N N N 2 H H Motuporamine A Motuporamine B 4 5 O O O O O O 6a 6b 7 Scheme 1 Cyclododecanone is also an important intermediate for synthesis of natural muscone 8 and macrocyclic fragrances of musk like odor e.g. (S)-muscolides: 9 and 10 as well as (R)-12- methyltridecanolide 11.6-10 In addition, it is also a starting material used for synthesis of the Page 430 ©ARKAT-USA, Inc. Reviews and Accounts ARKIVOC 2011 (i) 429-495 expensive compounds having the greatly appreciated woody-amber odor,11 such as Hydroxyambran® 12,12 and Lignoxan® 13,13 (Scheme 2). O O O O O (S)-muscone (8) (S)-muscolide (9)(S)-muscolide (10) O O OH O (R)-12-methyltridecanolide (11) Hydroxyambran® (12) Lignoxan® (13) Scheme 2 Besides, it is served as a precursor for preparation of 1,1-dihydroperoxy-cyclododecane (DOD) 14 which in turn used as starting material for synthesis of a series of antimalarial agents such as 15 and 16 (Scheme 3).14-18 OOMe 1- Ag2O, RI 2- Ag2O, MeI OOR OOH 15 1 OOH O CsOH, DMF O 14 ( )n I ( )n I O O 16 Scheme 3 1,1-Dihydroperoxy-cyclododecane (DOD) 14 is also proved to be a useful oxidizer applied in polynucleotide synthesis.19 Page 431 ©ARKAT-USA, Inc. Reviews and Accounts ARKIVOC 2011 (i) 429-495 B B O O O O O O CH2Cl2/EtOAc O P + 14 O P O O B O B NC O NC O O O Once more, Beckmann rearrangement of cyclododecanone oxime 17 into laurolactam 18 is a highly important industrial process, where ring opening polymerization of lactam 18 is used industrially for production of Nylon and its copolymers (Scheme 4).20 O NOH NH NH2OH.HCl Beckmann Polymerization 1 Naylon Pyridine / EtOH, rearrangement 17 18 Scheme 4 2. Synthesis of Cyclododecanone (1) Generally speaking, the twelve-membered ring is easily assembled through cyclotrimerization of butadiene 19. Butadiene cyclotrimerization process is performed in presence of various catalytic systems comprised transition metal compounds: Ti, Cr, Ni, Mn and organic compounds of aluminium.21-24 The butadiene cyclotrimerization product 1,5,9-cyclododecatriene 20 is the key intermediate for production of various twelve-membered ring systems belonging to different classes of organic compounds. In this context, 1,5,9-cyclododecatriene is easily converted into 1 in several ways (Scheme 5).25-35 Page 432 ©ARKAT-USA, Inc. Reviews and Accounts ARKIVOC 2011 (i) 429-495 Selective 19 Hydrogenation cyclotrimerization O 21 N2O Full O2 Hydrogenation B(OH)3 1 22 20 Oxidation O OH Epoxidation H2 Raney Nickle 23 24 Scheme 5 3. Chemistry of Cyclododecanone 3.1 Halogenation 2-Bromocyclododecanone 25 can be obtained almost in quantitative yield by using N- bromosuccinimide (NBS) under photochemical conditions.36 Bromoketone 25 is also prepared in an excellent yield using CuBr2 in a mixture of chloroform and ethyl acetate under stream of nitrogen gas.37 On the other hand, 1 can be regenerated by debromination of 25 through dithionite reduction of the pyridinium salt 26 (Scheme 6).38 O O Br N o NBS , hv , 30 C, Et2O, 2 h Pyridine/ Acetone 1 Br or 2 CuBr2, CHCl3 / EtOAc 25 26 Na2S2O8 / AcOH Scheme 6 Selective α-iodination of 1 was accomplished in the solid state within a very short reaction time with excellent yield using elemental iodine and oxone as a catalyst, by grinding in a mortar to afford 27.39 Iodoketone 27 is also prepared efficiently using elemental Iodine and hydrogen peroxide.40,41 Page 433 ©ARKAT-USA, Inc. Reviews and Accounts ARKIVOC 2011 (i) 429-495 While, α-chlorocyclododecanone 28 was achieved in very good yield via treatment of cyclododecanone 1 with LDA followed by p-toluenesulfonyl chloride.42 O R Y 1 RY 27: I Oxone, I2 28: Cl LDA, TsCl 3.2 Oxidation Cyclododecanone 1 was efficiently converted into the corresponding gem-dihydroperoxide 14 in high yield within a short period of time on treatment with aqueous H2O2 in the presence of catalytic 43-45 amount of CAN in acetonitrile at room temperature. While, treatment of 1 with H2O2 in fluorinated alcohol (HFIP) afforded the corresponding anti-malarial agent tetraoxane derivative 29 in 55% yield (Scheme 7).46 HOO OOH aq. H2O2 (50%), CAN (cat.) MeCN, rt, 1h 1 14 H2O2/ HBF4/ MTO O O HFIP OO 29 Scheme 7 The industrially important 1,12-dodecanedioic acid 31 is the major oxidation product of cyclododecanone dimethyl acetal 30 by in situ generated performic acid, besides the minor products 32 and 33.47 Page 434 ©ARKAT-USA, Inc. Reviews and Accounts ARKIVOC 2011 (i) 429-495 OH HO MeO OMe O 31 O + H2O2 / HCOOH HO OH 32 H SO 2 4 O + 30 HO OCHO 33 O While Gauthard et al. reported that 1,12-dodecanedioic acid 31 can be obtained by air oxidation of 1 in presence of metal-free and platinum loaded carbon catalysts.48 Alternatively, the diacid 31 is also obtained in 86% yield by oxidation of cyclododecanone 1 in presence of rhenium carbonyl and polyethylene glycol as phase transfer catalyst.49 In addition, the dibutyl ester of 31 was achieved by oxidation of 1 with hydrogen peroxide in butanol.50 OH air oxidation or HO 1 O O2/ Re(CO)10 , KOH O 31 K2CO3 , PEG-400, DME, r.t., 1atm Alternatively, 11-cyanoundecanoic acid 34 was obtained by reaction of 1 with sodium pentacano nitrosyl ferrate(II) (NP) under basic conditions to give a colored complex which underwent acid hydrolysis to give 34.51 + NP H COOH 1 Complex NC - OH 34 NP = Sodium pentacanonitrosylferrate(II) 1,2-Cyclododecanedione 38 was achieved in a good yield,52-54 by a variety of oxidation methodologies (Scheme 5): (a) by treatment of 1 with excess sodium nitrite and aq. HCl,55 (b) o through treatment of 2-hydroxycyclododecanone 35 with either DMSO/CF3COOH at -78 C or Cu(OAc)/AcOH, (c) when 2-bromo-cyclododecanone 25 is oxidized using DMSO in presence of KI/K2CO3. Moreover, 38 was also obtained through chemical or photochemical oxidation of 2- (methylthio)cyclododecanone 36,56 and 2-((dimethylamino)methylene)cyclododecanone 37,57 respectively (Scheme 8). Page 435 ©ARKAT-USA, Inc. Reviews and Accounts ARKIVOC 2011 (i) 429-495 O SMe aq. acetone CuCl2, CuO O 36 O Cu(OAc) / AcOH OH O O Br KI / K2CO3 DMSO / CH2Cl2 DMSO CF COOH 3 35 38 25 NaNO2 / HCl O2, hv dioxane O NMe2 1 37 Scheme 8 Altohyrtin C 39 was found to be exceedingly potent against human colon (HCT116) and ovarian (A2780) cell lines.58 OH OAc Me HO O OH HO OH O H O O O HO O Me (Altohyrtin C) MeO AcO 39 OH Me O Me O O OMe Cyclododecanone 1 is the source of 40 which is a main building block in the total synthesis of Altohyrtin C analogue 44 (Scheme 9).58 Page 436 ©ARKAT-USA, Inc. Reviews and Accounts ARKIVOC 2011 (i) 429-495 OHC CO2TIPS 1- TIPSCl, NaI, Et3N, MeCN 1 2- O3, MeOH, CH2Cl2 3- Me2S 40 OTBS OTBS OTES OTES TIPSO C O O 2 TESO MeLi, LiBr TESO OTES + 40 OTES MeO H MeO H Me Me O O TBSO TBSO Me Me PPh3I 41 42 OTBS OH 1- TBAF, THF, 0oC 2- 2,4,6-trichlorobenzoyl chloride, i-Pr2NEt 3- DMAP, Toluene, 90oC (16h) OH OH O O O O HO TESO O HF, MeCN, O MeO H MeO H Me o Me O -18 C O HO TBSO Me Me 44 43 Scheme 9 3.3 Alkylation of cyclododecanone Cyclododecanone 1 easily undergoes alkylation on its α-carbon under phase-transfer catalysis (PTC). β-Halopropionic aldehyde acetals 45a, b react readily with 1 to give the respective 2-(3- oxopropyl) cyclododecanone acetals 46a, b. Acid hydrolysis of acetals 46 resulted in formation of 12-hydroxybicyclo[9.3.1]pentadecan-15-one 48 probably formed due to intramolecular aldol condensation of ketoaldehyde 47.59 3-(2-Oxocyclododecyl)propionic acid and its esters are interesting starting materials for the synthesis of valuable aromatic substances such as decamethylene-8-valerolactone,60 pentadecanolide (exaltolide),61 and cyclopentadecanone (exaltone),62 as well as macrocyclic ketoimides and N-acetylketolactams.63 Accordingly, ω-(2- Page 437 ©ARKAT-USA, Inc.
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