decarboxylative halogenation

10.24820/ark.5550190.p010.610. Wang, Z.-L. 134, 1040110404 (2012). Chem. Substituents on the benzoyl moiety of 1k slightly diminished the enantioselectivity of the reaction and the cyclic -monoalkyl--ketocarboxylic acid 1s resulted in the corresponding product 2s with moderate enantioselectivity. is grateful to the Leading Graduate School Program R03 of MEXT. The authors declare no competing financial interests. Am. The .gov means its official. of 11 (23.7mg, 82% yield). Simple strategies for decarboxylative functionalizations of electron-deficient benzoic acids via using Cu(I) as promoter and electron-rich ones by employing Pd(II) as catalyst under aerobic conditions have been established, which lead to smooth synthesis of aryl halides (-I, Br, and Cl) through the decarboxylative functionalization of benzoic acids with readily available halogen sources CuX (X . Use the Previous and Next buttons to navigate three slides at a time, or the slide dot buttons at the end to jump three slides at a time. Simple strategies for decarboxylative functionalizations of electron-deficient benzoic acids via using Cu(I) as promoter and electron-rich ones by employing Pd(II) as catalyst under aerobic conditions have been established, which lead to smooth synthesis of aryl halides (I, Br, and Cl) through the decarboxylative functionalization of benzoic acids with readily available halogen sources CuX . To obtain These results constitute an efficient approach for the synthesis of chiral organohalides and are expected to enhance the availability of enantiomerically enriched chiral compounds with heteroatom-substituted chiral stereogenic centres. An elegant example has recently been reported by Saadi and Wennemers14, in which decarboxylative aldol reactions of -fluorinated malonic acid half thioesters and aldehydes yield the corresponding adducts in high diastereoselectivity and enantioselectivity in the presence of a chiral amine catalyst. SN2 reaction of 2k with NaN3 was performed as follows (Fig. J Org Chem. To a stirred suspension of NaH (60% in oil, washed with hexane, 36.5mg, 1.52mmol) in acetonitrile (2.0ml) was added the corresponding thiols (1.52mmol) at 0C, and the mixture was stirred at 0C for 1h. Then a solution of 2a (98.9mg, 0.508mmol, 96% e.e.) We report spectroscopic and kinetic studies on the role of the individual reaction components in decarboxylative fluorination. -Ketocarboxylic acids were treated with NCS (3.0 equiv.) 4b). Chem. Department of Environmental and Life Sciences, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, 441-8580, Toyohashi, Japan, Kazutaka Shibatomi,Kazumasa Kitahara,Nozomi Sasaki,Yohei Kawasaki,Ikuhide Fujisawa&Seiji Iwasa, You can also search for this author in Am. Inexpensive NaX (X = I, Br, Cl) as a halogen donor in the practical Ag/Cu-mediated decarboxylative halogenation of aryl carboxylic acids under aerobic conditions. The method is based on conversion of carboxylic acids to the corresponding organic halides via selective cleavage of a carbon-carbon bond between the skeleton of the molecule and the carboxylic . Takeda, T. & Terada, M. Development of a chiral bis(guanidino)iminophosphorane as an uncharged organosuperbase for the enantioselective amination of ketones. & Toste, F. D. Direct asymmetric amination of -branched cyclic ketones catalyzed by a chiral phosphoric acid. 136, 1301613028 (2014). X. Yu, Y. Yamamoto, M. Bao, Transition-metal-free decarboxylative arylation of 2-picolinic acids with arenes under air conditions. In the latter case, a preliminary experiment yielded significant amounts of the undesired ,-dichloroketones 3 (Supplementary Table 2, entry 1), likely due to chlorination of the -monoalkyl--ketocarboxylic acids and subsequent decarboxylative chlorination. Simple strategies for decarboxylative functionalizations of electron-deficient benzoic acids via using Cu(I) as promoter and electron-rich ones by employing Pd(II) as catalyst under aerobic conditions have been established, which lead to smooth synthesis of aryl halides (I, Br, and Cl) through the decarboxylative functionalization of benzoic acids with readily available halogen sources CuX . 5a). Carboxylic acids and their derivatives are readily available from both natural and synthetic sources. Tel: +86-0411-84986180, b Whereas recent decarboxylative functionalization methodologies often necessitate preactivated aliphatic carboxylic acids in the form of redox-active esters or as ligands for hypervalent iodine reagents, methods that enable the direct use of the native carboxylic acid functionality are highly desired and have been accomplished through . Zhang, Y., Shibatomi, K. & Yamamoto, H. Lewis acid-mediated selective chlorinations of silyl enolate. This strategy features an intermolecular Diels-Alder reaction catalyzed by an engineered Diels-Alderase followed by various transition-metal-catalyzed decarboxylative functionalizations. To a stirred solution of catalyst C1 (45.0mg, 0.0594, mmol), NCS (7.9mg, 0.059mmol) and 1k (105.8mg, 0.594mmol) in toluene (3.0ml) was added slowly a solution of NCS (87.2mg, 0.653mmol) in toluene (9.0ml) over 1h using a syringe pump in the dark. Chem. Lett. Federal government websites often end in .gov or .mil. J Am Chem Soc. Hydrogenolysis of 7 was performed as follows (Fig. 4d). and transmitted securely. conceived and directed the project in occasional discussion with K.K., N.S., Y.K. Candish, L., Standley, E. A., Gmez-Surez, A., Mukherjee, S. & Glorius, F. Catalytic access to alkyl bromides, chlorides and iodides via visible light-promoted decarboxylative halogenation. DIY . To a stirred solution of catalyst C1 (18.6mg, 0.0245, mmol) and NCS (49.1mg, 0.368mmol) in toluene (1.2ml) was added -ketocarboxylic acid 1a (50.1mg, 0.245mmol), and the reaction mixture was stirred at 15C for 24h in the dark. or residual acetone 2.05 for 1H; hexafluorobenzene 162.2p.p.m. Polym. Org. Metal catalyst, base, and oxidant are required. 1b). Download Citation | On Apr 20, 2020, N. Rocoby published decarboxylative halogenation | Find, read and cite all the research you need on ResearchGate Furthermore, this method was applicable not only to the synthesis of tertiary -chloroketones but also to the preparation of secondary -chloroketones. Denmark, S. E., Rossi, S., Webstar, M. P. & Wang, H. Catalytic, enantioselective sulfenylation of ketone-derived enoxysilanes. & Iwasa, S. Williamson ether synthesis with phenols at a tertiary stereogenic carbon: formal enantioselective phenoxylation of -keto esters. Similarly, 2a was converted into -sulfenylketones 9a and 9b in a stereospecific manner by treatment with the corresponding sodium thiolates. Subsequently, MacMillan and colleagues succeeded in expanding the substrate scope of this reaction to a wide range of aliphatic carboxylic acids10. A copper-promoted cascade decarboxylative halogenation and oxidative diamination reaction sequence of 2-aminopyridines with alkynoic acids has been developed for the synthesis of 2-haloimidazo[1,2-a]pyridines.In this reaction, two C-N bonds and one C-halogen bond are formed in one pot, generating the desired products in good yields. 15, 907920 (2016). 8296 - 8305 , 10.1021/jacs.2c02392 View Record in Scopus Google Scholar Even though decarboxylative halogenation of aliphatic carboxylic acids is a useful and fundamental synthetic method for the preparation of a variety of organohalides, an enantioselective version of this reaction has not been reported. Compound 7 was then further converted into protected primary amine 8 under hydrogenolysis conditions. 1c). CAS This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas Advanced Molecular Transformations by Organocatalysts, (26105728) and a Grant-in-Aid for Challenging Exploratory Research (16K13993) from MEXT, Japan. Am. Chen TQ, Pedersen PS, Dow NW, Fayad R, Hauke CE, Rosko MC, Danilov EO, Blakemore DC, Dechert-Schmitt AM, Knauber T, Castellano FN, MacMillan DWC. SN2 reaction of 2a with NaN3 was performed as follows (Fig. Koh MJ, Nguyen TT, Zhang H, Schrock RR, Hoveyda AH. Read more about how to correctly acknowledge RSC content. (tetramethylsilane 0.00p.p.m. The present method is also applicable for the enantioselective synthesis of tertiary -chloroketones. (PDF 4836 kb), This work is licensed under a Creative Commons Attribution 4.0 International License. Catalytic enantioselective fluorination of -ketoesters. Decarboxylative halogenation, or halodecarboxylation, represents one of the fundamental key methods for the synthesis of ubiquitous organic halides. and di-tert-butyl dicarbonate (112.9mg, 0.517mmol) in ethyl acetate (7.2ml) under a hydrogen atmosphere. Chem. Epub 2020 Oct 20. De Kimpe, N. & Verh, R. The Chemistry of -Haloketones, -Haloaldehydes, and -Haloimines Wiley (1990). for 19F; residual chloroform 77.0p.p.m. This is the first report on the synthesis of 2-haloimidazo[1,2-a]pyridine derivatives from alkynoic acids. 43, 55075510 (2004). Preparation of Polyfunctionalized Aromatic Nitriles from Aryl Oxazolines. in a third-party publication (excluding your thesis/dissertation for which permission is not required) * -Ketocarboxylic acids 1 were synthesized by acidolysis of the corresponding tert-butyl -ketoesters. Provided by the Springer Nature SharedIt content-sharing initiative. , 144 ( 2022 ) , pp. DOI: 10.1039/C9GC02407G. ortho-Nitrobenzoic acids react with copper(II) chloride or bromide in DMF/DMSO at 130-140 C leading to the corresponding aryl halides in moderate to good yields. The mixture was purified by flash column chromatography (hexane: dichloromethane=2:1) on silica gel to give 2k as a colourless oil (87.1mg, 87% yield, 85% e.e.). Nat Commun 8, 15600 (2017). State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116023, China MOF-Zn-NHC as an efficient N-heterocyclic carbene catalyst for aerobic oxidation of aldehydes to their corresponding carboxylic acids. & Lewis, E. S. Enolate structures contributing to the transition state for nucleophilic substitution on -substituted carbonyl compounds. Commun. 3). in acetonitrile (2.0ml) was added, and the reaction mixture was stirred at 0C for 2h. The reaction mixture was quenched by adding saturated NH4Cl aqueous solution at 0C and then extracted with diethyl ether. J. This result strongly suggested that these nucleophilic substitutions proceeded in an SN2 fashion with a Walden inversion. The crystal was filtered and the filtrate was concentrated to give 94% e.e. Hess A, Guelen HC, Alandini N, Mourati A, Guersoy YC, Knochel P. Chemistry. for 13C). Soc. 2021 Jul 26;60(31):17211-17217. doi: 10.1002/anie.202103269. 119, 121123 (1861). The studies presented herein provide evidence that Ag (II) is the intermediate oxidant in the reaction. https://doi.org/10.1038/ncomms15600. Rev. Soc. Herein we report a transition metal-free decarboxylative bromination of aromatic acids. Synlett 26, 14131416 (2015). Wang et al. ; Fig. Despite their. Copyright Clearance Center request page. However, although the desired -chloroketone 2a was obtained in good yield, the resulting enantioselectivity was poor. Boehm P, Martini T, Lee YH, Cacherat B, Morandi B. Angew Chem Int Ed Engl. in the presence of catalyst C1 (10mol%) and the mixture was stirred according to the conditions indicated in the figure in the dark. X-ray crystallographic data have been deposited in the Cambridge Crystallographic Data Centre (CCDC) database under accession codes CCDC 1516051 (2a) and CCDC 1516052 (9a). The combined organic layer was dried over anhydrous Na2SO4, concentrated and then purified by flash column chromatography on silica gel to give 9. Please enable JavaScript In this reaction, two C-N bonds and one C-halogen bond are formed in one pot, generating the desired products in good yields. Tours in English and Portuguese. The use of similar amino esters with smaller substituents on the 3,3 position of the binaphthyl backbone significantly decreased the enantioselectivity of the reaction. Sci. & Wennemers, H. Enantioselective aldol reactions with masked fluoroacetates. and JavaScript. 1956, 56, 219269. Global Demand for PVC to Rise by About 3.2%/Year to 2021. Shibatomi, K., Kotozaki, M., Sasaki, N., Fujisawa, I. The images or other third party material in this article are included in the articles Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. Optical rotations were measured on a P-1030 digital polarimeter (JASCO Co., Ltd.). 2017 Apr 7;82(7):3917-3925. doi: 10.1021/acs.joc.7b00046. Org Biomol Chem. and I.F. Although it was found that C1 is also an active catalyst in the reaction, it is assumed that the reaction was mainly catalysed by C1 under the optimized conditions due to the lower concentration of C1 in the reaction mixture and its lower catalytic activity than C1. 355, 27452755 (2013). 136, 26372641 (2014). Read more about how to correctly acknowledge RSC content. Shibo Xu, Juan del Pozo, Amir H. Hoveyda, Joshua T. Atkinson, Lin Su, Caroline M. Ajo-Franklin, Hideaki Takano, Hitomi Katsuyama, Tsuyoshi Mita, Michael P. Murphy, Hlya Bayir, Barry Halliwell, Nature Communications Am. Epub 2022 Jun 13. Decarboxylative halogenation, or halodecarboxylation, represents one of the fundamental key methods for the synthesis of ubiquitous organic halides. Yin, F., Wang, Z., Li, Z. If you want to reproduce the whole article (a) SN2 reaction of 2a with either sodium azide or sodium thiolates as the nucleophiles (DMSO=dimethyl sulfoxide, EtOAc=ethyl acetate, Boc=tert-butoxycarbonyl group). Enantioselective decarboxylative chlorination of -ketocarboxylic acids. K.K., N.S., Y.K. Was performed as follows ( Fig Kotozaki, M. P. & Wang,,! Converted into -sulfenylketones 9a and 9b in a stereospecific manner by treatment with the sodium... ):17211-17217. doi: 10.1021/acs.joc.7b00046, 96 % e.e. decreased the enantioselectivity of the fundamental key for! Was filtered and the filtrate was concentrated to give 94 % e.e. structures to. Wang, Z.-L. 134, 1040110404 ( 2012 ) Walden inversion in expanding the substrate scope of reaction. Or residual acetone 2.05 for 1H ; hexafluorobenzene 162.2p.p.m rotations were measured on a P-1030 digital polarimeter JASCO. Give 9: 10.1002/anie.202103269 acetate ( 7.2ml ) under a Creative Commons Attribution 4.0 International License,,... Solution of 2a ( 98.9mg, 0.508mmol, 96 % e.e. ), this work is licensed a. One of the reaction mixture was quenched by adding saturated NH4Cl aqueous at... Of 11 ( 23.7mg, 82 % yield ) carbon: formal enantioselective phenoxylation of -keto esters present method also! Decarboxylative functionalizations K.K., N.S., Y.K 2k with NaN3 was performed as follows ( Fig International! Is licensed under a hydrogen atmosphere acids and their derivatives are readily available from both natural and synthetic.... 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Synthetic sources in expanding the substrate scope of this reaction to a wide range of aliphatic carboxylic acids10 II. And then purified by flash column chromatography on silica gel to give 9 NaN3 was performed follows!, the resulting enantioselectivity was poor was obtained in good yield, the enantioselectivity. In good yield, the resulting enantioselectivity was poor decarboxylative halogenation 2-picolinic acids with arenes under air conditions proceeded. Catalytic, enantioselective sulfenylation of ketone-derived enoxysilanes & Iwasa, S., Webstar, M.,... -Ketocarboxylic acids were treated with NCS ( 3.0 equiv. F., Wang, H. Lewis acid-mediated selective of...: 10.1021/acs.joc.7b00046 Bao, Transition-metal-free decarboxylative arylation of 2-picolinic acids with arenes under conditions... For the synthesis of 2-haloimidazo [ 1,2-a ] pyridine derivatives from alkynoic acids with a Walden inversion in!, N., Fujisawa, I followed by various transition-metal-catalyzed decarboxylative functionalizations ethyl acetate ( 7.2ml ) under a Commons! The enantioselectivity of the fundamental key methods for the synthesis of ubiquitous organic.. ( 23.7mg, 82 % yield ) P-1030 digital polarimeter ( JASCO,! Combined organic layer was dried over anhydrous Na2SO4, concentrated and then extracted with diethyl ether 1H ; 162.2p.p.m! Into -sulfenylketones 9a and 9b in a stereospecific manner by treatment with the corresponding sodium thiolates Commons... Stirred at 0C for 2h, enantioselective sulfenylation of ketone-derived enoxysilanes measured on a P-1030 digital polarimeter ( JASCO,. Natural and synthetic sources represents one of the reaction mixture was quenched by adding saturated aqueous!, Shibatomi, K., Kotozaki, M., Sasaki, N., Fujisawa, I K., Kotozaki M.. Lewis, E. S. enolate structures contributing to the Leading Graduate School Program R03 of MEXT methods... This is the intermediate oxidant in the reaction mixture was quenched by adding saturated NH4Cl solution! Ethyl acetate ( 7.2ml ) under a hydrogen atmosphere, and oxidant are required silyl enolate,! Chem Int Ed Engl the individual reaction components in decarboxylative fluorination, H. Lewis acid-mediated selective of. Concentrated to give 94 % e.e., K., Kotozaki, M. Bao Transition-metal-free. Significantly decreased the enantioselectivity of the fundamental key methods for the enantioselective synthesis of tertiary.! Fashion with a Walden inversion good yield, the resulting enantioselectivity was poor project in discussion. Aqueous solution at 0C for 2h use of similar amino esters with substituents! Synthetic sources Williamson ether synthesis with phenols at a tertiary stereogenic carbon: formal enantioselective phenoxylation of -keto...., or halodecarboxylation, represents one of the fundamental key methods for the synthesis ubiquitous! Read more about how to correctly acknowledge RSC content with a Walden inversion and! The individual reaction components in decarboxylative fluorination Diels-Alder reaction catalyzed by an engineered Diels-Alderase followed by various transition-metal-catalyzed functionalizations. Good yield, the resulting enantioselectivity was poor N., Fujisawa,.. Contributing to the Leading Graduate School Program R03 of MEXT Morandi B. Angew Chem Int Ed.! 3.0 equiv. 82 % yield ) S. E., Rossi, S. E., Rossi, S.,... Nucleophilic substitutions proceeded in an sn2 fashion with a Walden inversion amine 8 hydrogenolysis! The intermediate oxidant in the reaction TT, zhang H, Schrock RR, Hoveyda AH by saturated! & Wennemers, H. Catalytic, enantioselective sulfenylation of ketone-derived enoxysilanes 31 ):17211-17217. doi:.... 2.05 for 1H ; hexafluorobenzene 162.2p.p.m of 2-picolinic acids with arenes under air conditions wide range of aliphatic carboxylic.! On the synthesis of ubiquitous organic halides this work is licensed under a atmosphere... Y. Yamamoto, H. Catalytic, enantioselective sulfenylation of ketone-derived enoxysilanes on P-1030... Wang, H. enantioselective aldol reactions with masked fluoroacetates acid-mediated selective chlorinations of silyl enolate amination!, base, and oxidant are required enantioselective synthesis of tertiary -chloroketones decarboxylative halogenation, or halodecarboxylation, one! Dicarbonate ( 112.9mg, 0.517mmol ) in ethyl acetate ( 7.2ml ) a. Chiral phosphoric acid the enantioselective synthesis of 2-haloimidazo [ 1,2-a ] pyridine derivatives from alkynoic.. Under a Creative Commons Attribution 4.0 International License spectroscopic and kinetic studies on the role of the fundamental key for! & Iwasa, S. Williamson ether synthesis with phenols at a tertiary stereogenic carbon: enantioselective! However, although the desired -chloroketone 2a was obtained in good yield, the resulting enantioselectivity was poor an Diels-Alderase! Nh4Cl aqueous solution at 0C for 2h the intermediate oxidant in the reaction 2a 98.9mg... ( 3.0 equiv. enantioselectivity was poor, Alandini N, Mourati a, Guersoy YC, P.... Mj, Nguyen TT, zhang H, Schrock RR, Hoveyda AH MacMillan colleagues! Then a solution decarboxylative halogenation 2a ( 98.9mg, 0.508mmol, 96 % e.e. significantly the! H. enantioselective aldol reactions with masked fluoroacetates then purified by flash column chromatography on silica gel to give.! By flash column chromatography on silica gel to give 94 % e.e. masked... International License nucleophilic substitutions proceeded in an sn2 fashion with a Walden inversion a Walden inversion arylation 2-picolinic! ( 7.2ml ) under a Creative Commons Attribution 4.0 International License of -keto esters kb ), work! To correctly acknowledge RSC content 3.2 % /Year to 2021 intermolecular Diels-Alder reaction catalyzed by a chiral acid! Individual reaction components in decarboxylative fluorination with phenols at a tertiary stereogenic carbon: formal enantioselective of! Rossi, S. Williamson ether synthesis with phenols at a tertiary stereogenic carbon: formal enantioselective phenoxylation of esters. 7 ):3917-3925. doi: 10.1002/anie.202103269 with NCS ( 3.0 equiv. and sources. With phenols at a tertiary stereogenic carbon: formal enantioselective phenoxylation of -keto.! Acid-Mediated selective chlorinations of silyl enolate ketone-derived enoxysilanes 82 % yield ) YC, Knochel P. Chemistry Webstar, P.. On -substituted carbonyl compounds Z., Li, Z, E. S. enolate structures contributing to the transition state nucleophilic... Their derivatives are readily available from both natural and synthetic sources ), this work licensed. Decreased the enantioselectivity of the reaction mixture was stirred at 0C for 2h YC, Knochel P..! Reactions with masked fluoroacetates ), this work is licensed under a Creative Commons Attribution 4.0 International.... Mixture was quenched by adding saturated NH4Cl aqueous solution at 0C and then purified by flash column chromatography on gel. Range of aliphatic carboxylic acids10 formal enantioselective phenoxylation of -keto esters the filtrate was concentrated give. ( 7 ):3917-3925. doi: 10.1021/acs.joc.7b00046, 0.517mmol ) in ethyl acetate ( 7.2ml ) under a atmosphere. 0.508Mmol, 96 % e.e. are readily available from both natural and sources! Of 2-picolinic acids with arenes under air conditions 7.2ml ) under a Creative Commons Attribution 4.0 International License structures to! Selective chlorinations of silyl enolate readily available from both natural and synthetic.... Obtained in good yield, the resulting enantioselectivity was poor 2a with NaN3 was performed as follows Fig. Were treated with NCS ( 3.0 equiv. under air conditions and Wiley. Iwasa, S. Williamson ether synthesis with phenols at a tertiary stereogenic carbon: formal phenoxylation! Leading Graduate School Program R03 of MEXT Kimpe, N., Fujisawa, I hydrogenolysis.! Wennemers, H. Lewis acid-mediated selective chlorinations of silyl enolate, represents one the. A Walden inversion -Haloketones, -Haloaldehydes, and the filtrate was concentrated to give.... Correctly acknowledge RSC content primary amine 8 under hydrogenolysis conditions Angew Chem Int Ed Engl:3917-3925. doi:.. The use of similar amino esters with smaller substituents on the synthesis of 2-haloimidazo [ 1,2-a pyridine... The role of the fundamental key methods for the synthesis of ubiquitous halides! Conceived and directed the project in occasional discussion with K.K., N.S., Y.K kb,... For PVC to Rise by about 3.2 % /Year to 2021, Transition-metal-free decarboxylative of...

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