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Phosphonium coupling is a chemical reaction in organic chemistry for organic synthesis. It is a mild, efficient, chemoselective and versatile methodology for the direct C–C, C–N, C–O, and C–S bond formations of unactivated and unprotected tautomerizable heterocycles. ==History== Originally reported in 2004,〔Kang, Fu-An; Murray, William V., Efficient conversion of Biginelli-type 3,4-dihydropyrimidin-2(1H)-ones to pyrimidines via in-situ activation using PyBroP, Abstracts of Papers, 228th ACS National Meeting, Philadelphia, PA, United States, August 22–26, 2004 (2004), ORGN-702.〕 phosphonium coupling proceeds via C–OH bond activation of a tautomerizable heterocycle with a phosphonium salt (PyBroP, PyBOP, BroP, or BOP), and subsequent functionalization with either a nucleophile through SNAr displacement or an organometallic through transition metal catalyzed cross coupling reaction.〔Kang, Fu-An; Kodah, Jason; Guan, Qunying; Li, Xiaobing; Murray, William V., Efficient conversion of Biginelli 3,4-dihydropyrimidin-2(1H)-one to pyrimidines via PyBroP-mediated coupling, Journal of Organic Chemistry (2005), 70(5), 1957-1960. 〕〔Kang, Fu-An; Sui, Zhihua; Murray, William V., Pd-Catalyzed direct arylation of tautomerizable heterocycles with aryl boronic acids via C-OH bond activation using phosphonium salts, Journal of the American Chemical Society (2008), 130(34), 11300-11302. 〕〔Kang, Fu-An; Sui, Zhihua; Murray, William V., Phosphonium coupling in the direct bond formations of tautomerizable heterocycles via C-OH bond activation, European Journal of Organic Chemistry (2009), (4), 461-479. 〕〔Kang, Fu-An; Lanter, James C.; Cai, Chaozhong; Sui, Zhihua; Murray, William V., Direct dehydrative cross-coupling of tautomerizable heterocycles with alkynes via Pd/Cu catalyzed phosphonium coupling, Chemical Communications (Cambridge, United Kingdom) (2010), 46(8), 1347-1349. 〕 As the first direct bond formation via C–OH bond activation, phosphonium coupling offers a powerful and practical methodology for chemical synthesis that features operational simplicity, functionality compatibility, and broad substrate scope. Its attractive protecting group free direct bond formation involving a domino multiple-step process in a single step provides unique and facile access to many biologically important heterocycles.〔Wan, Zhao-Kui; Binnun, Eva; Wilson, Douglas P.; Lee, Jinbo, A Highly Facile and Efficient One-Step Synthesis of N6-Adenosine and N6-2'-Deoxyadenosine Derivatives, Organic Letters (2005), 7(26), 5877-5880.〕〔S. Bae, M. K. Lakshman, J. Am. Chem. Soc. 2007, 129, 782.〕〔Shi, Ce; Aldrich, Courtney C. Efficient Pd-Catalyzed Coupling of Tautomerizable Heterocycles with Terminal Alkynes via C-OH Bond Activation Using PyBrOP, Organic Letters (2010), 12(10), 2286-2289.〕〔Mehta, Vaibhav P.; Modha, Sachin G.; Van der Eycken, Erik V., Microwave-Assisted Palladium-Catalyzed Phosphonium Coupling of 2(1H)-Pyrazinones, Journal of Organic Chemistry (2010), 75(3), 976-979.〕〔Radl, Stanislav; Blahovcova, Michaela; Tkadlecova, Marcela; Havlicek, Jaroslav, Synthetic studies connected with the preparation of N--N-ethylacetamide, a zaleplon regioisomer, Heterocycles (2010), 80(2), 1359-1379.〕〔Li, Shui-Ming; Huang, Jie; Chen, Guo-Jun; Han, Fu-She, PdCl2(dppf)-catalyzed in situ coupling of 2-hydroxypyridines with aryl boronic acids mediated by PyBroP and the one-pot chemo- and regioselective construction of two distinct aryl-aryl bonds, Chemical Communications (Cambridge, United Kingdom) (2011), 47(48), 12840-12842.〕〔El Marrouni, Abdelatif; Fabrellas, Josep M.; Heras, Montserrat, Coupling reaction between electron-rich pyrimidinones and α-amino acids promoted by phosphonium salts, Organic & Biomolecular Chemistry (2011), 9(17), 5967-5977.〕 The concept of in situ activation of the C-OH bond in phosphonium coupling has also been applied to cross coupling reactions of tautomerizable heterocycles and arenols using other types of activating reagents.〔Ackermann, Lutz; Mulzer, Michael, Dehydrative Direct Arylations of Arenes with Phenols via Ruthenium-Catalyzed C-H and C-OH Bond Functionalizations, Organic Letters (2008), 10(21), 5043-5045.〕〔Singer, Robert A.; Dore, Michael, Practical amination of nitropyridones by silylation, Organic Process Research & Development (2008), 12(6), 1261-1264.〕〔Luo, Yong; Wu, Jie, Copper-free Sonogashira reactions of 4-hydroxycoumarins with alkynes, Tetrahedron (2009), 65(34), 6810-6814.〕〔Peng, Yi-Yuan; Wen, Yanfang; Mao, Xuechun; Qiu, Guanyinsheng, Direct sulfanylation of 4-hydroxycoumarins with thiols in water, Tetrahedron Letters (2009), 50(20), 2405-2406.〕〔Zhao, Yu-Long; Li, You; Li, Yu; Gao, Lian-Xun; Han, Fu-She, Aryl Phosphoramides: Useful Electrophiles for Suzuki-Miyaura Coupling Catalyzed by a NiCl2/dppp System (dppp=1,3-Bis(diphenylphosphino)propane), Chemistry--A European Journal (2010), 16(17), 4991-4994.〕〔Shen, Zhen-Lu; He, Xiao-Fei; Hong, Yi-Ming; Hu, Xin-Quan; Mo, Wei-Min; Hu, Bao-Xiang; Sun, Nan, One-pot synthesis of 4-aminoquinazolines by hexamethyldisilazane-mediated reaction of quinazolin-4(3H)-ones with amines, Synthetic Communications (2011), 41(24), 3644-3653.〕〔Wang, Xi-Cun; Yang, Guo-Jun; Jia, Xiao-Dong; Zhang, Zhang; Da, Yu-Xia; Quan, Zheng-Jun, Synthesis of C2-functionalized pyrimidines from 3,4-dihydropyrimidin-2(1H)-ones by the Mitsunobu coupling reaction, Tetrahedron (2011), 67(18), 3267-3272.〕〔Hu, Yi; Ding, Qiuping; Ye, Shengqing; Peng, Yiyuan; Wu, Jie, Rapid access to 4-substituted-pyrones and 2(5H)-furanones via a palladium-catalyzed C-OH bond activation, Tetrahedron (2011), 67(38), 7258-7262.〕〔Shen, Zhenlu; He, Xiaofei; Dai, Jialiang; Mo, Weimin; Hu, Baoxiang; Sun, Nan; Hu, Xinquan, An efficient HCCP-mediated direct amination of quinazolin-4(3H)-ones, Tetrahedron (2011), 67(9), 1665-1672.〕〔Deng, Xiaohu; Roessler, Armin; Brdar, Ivana; Faessler, Roger; Wu, Jiejun; Sales, Zachary S.; Mani, Neelakandha S., Direct, metal-free amination of heterocyclic amides/ureas with NH-heterocycles and N-substituted anilines in POCl3, Journal of Organic Chemistry (2011), 76(20), 8262-8269.〕 The phosphonium salts have been traditionally used for peptide synthesis. Recently, besides their novel uses in phosphonium coupling, they have also found similar utilities in certain cross coupling reactions.〔Londregan, Allyn T.; Jennings, Sandra; Wei, Liuqing, Mild Addition of Nucleophiles to Pyridine-N-Oxides, Organic Letters (2011), 13(7), 1840-1843.〕 Phosphonium coupling generates in situ a pseudo aryl or heteroaryl halide (the intermediate phosphonium species), and subsequently reacts with the other coupling partners under the suitable conditions. Therefore, as a new addition to the modern chemical methodology toolbox, it can be applied to many classical reactions involving aryl or heteroaryl halides.〔Young, Ian S.; Baran, Phil S., Protecting-group-free synthesis as an opportunity for invention, Nature Chemistry (2009), 1(3), 193-205. 〕〔Goossen, Lukas J.; Goossen, Kaethe; Stanciu, Corneliu, C(aryl)-O Activation of Aryl Carboxylates in Nickel-Catalyzed Biaryl Syntheses, Angewandte Chemie, International Edition (2009), 48(20), 3569-3571. 〕〔McGlacken, Gerard P.; Bateman, Lorraine M., Chemical Society Reviews (2009), 38(8), 2447-2464. 〕〔Afagh, Nicholas A.; Yudin, Andrei K., Chemoselectivity and the Curious Reactivity Preferences of Functional Groups, Angewandte Chemie, International Edition (2010), 49(2), 262-310. 〕〔Mansour, Tarek S.; Bardhan, Sujata; Wan, Zhao-Kui, Phosphonium- and benzotriazolyloxy-mediated bond-forming reactions and their synthetic applications, Synlett (2010), (8), 1143-1169. 〕〔Yu, Da-Gang; Li, Bi-Jie; Shi, Zhang-Jie, Exploration of New C-O Electrophiles in Cross-Coupling Reactions, Accounts of Chemical Research (2010), 43(12), 1486-1495. 〕〔Chinchilla, Rafael; Najera, Carmen, Recent advances in Sonogashira reactions, Chemical Society Reviews (2011), 40(10), 5084-5121. 〕〔Sellars, Jonathan D.; Steel, Patrick G., Transition metal-catalysed cross-coupling reactions of P-activated enols, Chemical Society Reviews (2011), 40(10), 5170-5180. 〕〔Li, Bi-Jie; Yu, Da-Gang; Sun, Chang-Liang; Shi, Zhang-Jie, Activation of "Inert" Alkenyl/Aryl C=O Bond and Its Application in Cross-Coupling Reactions, Chemistry--A European Journal (2011), 17(6), 1728-1759. 〕〔Katritzky, Alan R.; Rachwal, Stanislaw, Synthesis of heterocycles mediated by benzotriazole. 2. Bicyclic systems, Chemical Reviews (Washington, DC, United States) (2011), 111(11), 7063-7120. 〕〔Ackermann, Lutz, Carboxylate-Assisted Transition-Metal-Catalyzed C-H Bond Functionalizations: Mechanism and Scope, Chemical Reviews (Washington, DC, United States) (2011), 111(3), 1315-1345. 〕〔Allen, Anna E.; MacMillan, David W. C., Synergistic catalysis: A powerful synthetic strategy for new reaction development, Chemical Science (2012), 3(3), 633-658. 〕 抄文引用元・出典: フリー百科事典『 ウィキペディア（Wikipedia）』 ■ウィキペディアで「Phosphonium coupling」の詳細全文を読む スポンサード リンク
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