Advances in Organic Reactions Using Phosphorus Acid as Reducing Agent

doi:10.6023/cjoc202404015

Abstract

Organic reduction reactions are one of the most basic chemical reactions, which are widely used in the synthesis of pharmaceuticals, agriculture chemicals, dye industry and fine chemicals. Common reducing agents mainly include hydrogen, metallic compounds (borohydride, lithium aluminum hydride, alkyl aluminium and low-valence metals, etc.), active metals, silane and hydrazine. Phosphorus acid is a common chemical in industry, it is also cheap, easy to access, and easy to use. At present, reactions using phosphorus acid as reducing agents usually do not require transition-metals, and has the advantages of low-cost, simple conditions and simple work-up procedures. However, compared with the extensive application of those common reducing agents in organic reduction reactions, the organic reactions using phosphorus acid as reducing agent are very limited. Organic reduction reactions which are using phosphorus acid as reducing agent are summarized from aspects of reaction type, the scope of substrate and reaction mechanism. Prospects in this field are also discussed.

Key words: phosphorus acid, iodine, reducing agent, reduction reaction, metal-free

Cite this article

Jing Xiao, Yuxiang Xie, Libiao Han. Advances in Organic Reactions Using Phosphorus Acid as Reducing Agent[J]. Chinese Journal of Organic Chemistry, 2024, 44(12): 3702-3712.

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Fig. & Tab. 22

Scheme 1. Tautomerization of phosphorus acid and its advan- tages as a reducing agent

Scheme 2. Deoxygenation of alcohols

Scheme 3. Deoxygenation of aromatic ketones

Scheme 4. Mechanism of deoxygenation of aromatic ketones

Scheme 5. Deoxygenation of phenylglyoxylic acid

Scheme 6. Deoxygenation of aromatic aldehydes

Scheme 7. Reductive iodination of aromatic aldehydes

Scheme 8. Deoxygenation of nitroarenes

Scheme 9. Reduction of phosphine oxides and phosphine chalcogenides

Scheme 9. Selective reduction of bidentate phosphine oxides

Scheme 11. Plausible reaction paths of the reduction phosphine oxides

Scheme 12. Deoxygenation of sulfoxide

Scheme 13. Mechanism of the dehalogenation of benzyl halides

Scheme 14. Benzylation of arenes with benzyl halides

Scheme 15. Benzylation of arenes involving aromatic aldehydes

Scheme 16. Intromolecular coupling reaction via deoxygenation of aromatic aldehydes

Scheme 17. Preparation of N-benzyl benzo heterocyclic ketones from aromatic aldehydes

Scheme 18. Reaction path

Scheme 19. Preparation of phosphines from the reductive coupling of aldehydes and P(O)-H compounds

Scheme 20. Mechanism of preparation of phosphines

Scheme 21. Preparation of phosphine oxides from the reductive coupling of aldehydes and P(O)-H compounds

Scheme 22. Reduction of coenzyme NAD＋ with phosphorus acid

References 66

[1]	Hu Y.-F.; Lin G.-Q. Modern Organic Reactions: Reduction, Chemical Industry Press, Beijing, 2013 (in Chinese).
	(胡跃飞, 林国强, 现代有机反应: 还原反应, 化学工业出版社, 北京, 2013.)
[2]	Irrgang T.; Kempe R. Chem. Rev. 2020, 120, 9583.
[3]	(a) Chung J. Y. L.; Meng D.; Shevlin M.; Gudipati V.; Chen Q.; Liu Y.; Lam Y.-H.; Dumas A.; Scott J.; Tu Q.; Xu F. J. Org. Chem. 2020, 85, 994. doi: 10.1021/acs.joc.9b02948 pmid: 31850754
	(b) Ashby E. C.; Boone J. R. J. Am. Chem. Soc. 1976, 98, 5524. pmid: 31850754
	(c) Heinsohn G. E.; Ashby E. C. J. Org. Chem. 1973, 38, 4232. pmid: 31850754
[4]	(a) Aqad E.; Lakshmikantham M. V.; Cava M. P. Org. Lett. 2004, 6, 3039.
	(b) Bueno-López A.; García-García A.; Illán-Gómez M. J.; Linares-Solano A.; Lecea C. S.-M. D. Ind. Eng. Chem. Res. 2007, 46, 3891.
[5]	Dams R.; Malinowski M.; Westdorp I.; Geise H. J. Org. Chem. 1982, 47, 248.
[6]	Pesti J.; Larson G. L. Org. Process Res. Dev. 2016, 20, 1164.
[7]	Espinosa J. C.; Navalon S.; Alvaro M.; Dhakshinamoorthy A.; Garcia H. ACS Sustainable Chem. Eng. 2018, 6, 5607.
[8]	Gerhard B.; Werner K.; Gerhard R.; Thomas H. Phosphorus Compounds, Inorganic, Wiley-VCH, Weinheim, 2000.
[9]	Liang X.-S.; Xiao Y.; Wu L.-Q. CN 103708433, 2013.
[10]	Zhang L.; Koreeda M. J. Am. Chem. Soc. 2004, 126, 13190.
[11]	Dai X.-J.; Li C.-J. J. Am. Chem. Soc. 2016, 138, 5433.
[12]	Robins M. J.; Wilson J. S.; Hansske F. J. Am. Chem. Soc. 1983, 105, 4059.
[13]	Milne J. E.; Storz T.; Colyer J. T.; Thiel O. R.; Seran M. D.; Larsen R. D.; Murry J. A. J. Org. Chem. 2011, 76, 9519.
[14]	West C. T.; Donnelly S. J.; Kooistra D. A.; Doyle M. P. J. Org. Chem. 1973, 38, 2675.
[15]	Clemmensen E. Chem. Ber. 1913, 46, 1837.
[16]	Bradlow H. L.; VanderWerf C. A. J. Am. Chem. Soc. 1947, 69, 1254.
[17]	Huang M. J. Am. Chem. Soc. 1949, 71, 3301.
[18]	Hutchins R. O.; Maryanoff B.; Milewski C. J. Am. Chem. Soc. 1971, 93, 1793.
[19]	(a) Blackwell J.; Hickinbottom W. J. J. Chem. Soc. 1961, 1405.
	(b) Gribble G.W.; Kelly W. J.; Emery S. E. Synthesis 1978, 763.
	(c) Ketcha D. M.; Lieurance B. A.; Homan D. F. J.; Gribble G. W. J. Org. Chem. 1989, 54, 4350.
[20]	(a) Kelly T. R.; Kim M. H. J. Am. Chem. Soc. 1994, 116, 7072.
	(b) Srikrishna A.; Viswajanani R.; Sattigeri J. A.; Yelamaggad C. V. Tetrahedron Lett. 1995, 36, 2347.
[21]	(a) Smonou I. Tetrahedron Lett. 1994, 35, 2071. pmid: 12467433
	(b) Fry J. L.; Orfanopoulos M.; Adlington M. G.; Dittman W. P.; Silverman S. B. J. Org. Chem. 1978, 43, 374. pmid: 12467433
	(c) Chandrasekhar S.; Reddy C. R.; Babu B. N. J. Org. Chem. 2002, 67, 9080. pmid: 12467433
[22]	(a) Lee W. Y.; Park C. H.; Kim H. J.; Kim S. J. Org. Chem. 1994, 59, 878.
	(b) Lee W. Y.; Park C. H.; Kim Y. D. J. Org. Chem. 1992, 57, 4074.
[23]	(a) Prakash G. K. S.; Do C.; Mathew T.; Olah G. A. Catal. Lett. 2011, 141, 507.
	(b) Sakai N.; Nagasawa K.; Ikeda R.; Nakaike Y.; Konakahara T. Tetrahedron Lett. 2011, 52, 3133.
	(c) Jumbam N. D.; Makaluza S.; Masamba W. Bull. Chem. Soc. Ethiop. 2018, 32, 179.
[24]	Deng J.; Xiao J.; Wang X.; Luo H.; Jia Z.; Wang J. Tetrahedron 2022, 113, 132755.
[25]	Savela R.; Wärnå J.; Murzin D. Y.; Leino R. Catal. Sci. Technol. 2015, 5, 2406.
[26]	Li Z.; Sheng C.; Yang C.; Qiu H. Org. Prep. Proced. Int. 2007, 39, 608.
[27]	Keinan E.; Perez D.; Sahai M.; Shvily R. J. Org. Chem. 1990, 55, 2927.
[28]	Bhor M. D.; Panda A. G.; Nandurkar N. S.; Bhanage B. M. Tetrahedron Lett. 2008, 49, 6475.
[29]	Zeng C.; Shen G.; Yang F.; Chen J.; Zhang X.; Gu C.; Zhou Y.; Fan B. Org. Lett. 2018, 20, 6859.
[30]	Lv F.; Xiao J.; Xiang J.; Guo F.; Tang Z.-L.; Han L.-B. J. Org. Chem. 2021, 86, 3081.
[31]	He T.; Zhang C.; Zhang L.; Du A. Nano Res. 2019, 12, 1817.
[32]	Liu W. J.; Qian T. T.; Jiang H. Chem. Eng. J. 2014, 236, 448.
[33]	(a) Kandagatla B.; Raju V. V. N. K. V. P.; Reddy G. M.; Rao S. C.; Iqbal J.; Bandichhor R.; Oruganti S. Tetrahedron Lett. 2012, 53, 7125.
	(b) Larock R. C. Comprehensive Organic Transformations, John Wiley & Sons, New York, 1999.
[34]	Krapcho J.; Turk C. F.; Piala J. J. J. Med. Chem. 1968, 11, 361. pmid: 4174063
[35]	(a) Formenti D.; Ferretti F.; Scharnagl F. K.; Beller M. Chem. Rev. 2019, 119, 2611. doi: 10.1021/acs.chemrev.8b00547 pmid: 30516963
	(b) Wang J.; Zhang Y. J.; Diao J. Y.; Zhang J.; Liu H.; Su D. Chin. J. Catal. 2018, 39, 79. doi: 10.1016/S1872-2067(17)62925-5 pmid: 30516963
[36]	Wu G. G.; Chen F. X.; LaFrance D.; Liu Z.; Greene S. G.; Wong Y.-S.; Xie J. Org. Lett. 2011, 13, 5220.
[37]	(a) Quin L. D. A Guide to Organophosphorus Chemistry, Wiley, New York, 2000.
	(b) Kamer P. C. J.; van Leeuwen P. W. N. M. Phosphorus(III) Ligands in Homogeneous Catalysis: Design and Synthesis, Wiley, Chichester, U.K., 2012.
[38]	Broger E. A.; Switzerland M. US 4249023, 1981.
[39]	Kuroboshi M.; Yano T.; Kamenoue S.; Kawakubo H.; Tanaka H. Tetrahedron 2011, 67, 5825.
[40]	Natoli J. G.; Parlin N. J. US 3405180, 1968.
[41]	Vilas M. C.; Parlin N. J. US 3855310, 1974.
[42]	Xiao J.; Wang J.; Zhang H.; Zhang J.; Han L.-B. J. Org. Chem. 2023, 88, 3909.
[43]	McGarrigle E. M.; Myers E. L.; Illa O.; Shaw M. A.; Riches S. L.; Aggarwal V. K. Chem. Rev. 2007, 107, 5841. doi: 10.1021/cr068402y pmid: 18072810
[44]	(a) Jang Y.; Kim K. T.; Jeon H. B. J. Org. Chem. 2013, 78, 6328;
	(b) Sanz R.; Escribano J.; Aguado R.; Pedrosa M. R.; Arnáiz F. J. Synthesis 2004, 35, 1629.
[45]	Ding F.; Jiang Y.; Gan S.; Bao R. L. Y.; Lin K.; Shi L. Eur. J. Org. Chem. 2017, 2017, 3427.
[46]	Enthaler S.; Krackl S.; Irran E.; Inoue S. Catal. Lett. 2012, 142, 1003.
[47]	García N.; Fernandez-Rodriguez M. A.; Garcia-Garcia P.; Pedrosa M. R.; Arnaiz F. J.; Sanz R. RSC Adv. 2016, 6, 27083.
[48]	(a) Alonso F.; Beletskaya I. P.; Yus M. Chem. Rev. 2002, 102, 4009.
	(b) Chelucci G.; Baldino S.; Pinna G. A.; Pinna G. Curr. Org. Chem. 2012, 16, 2921.
[49]	(a) Inoue K.; Sawada A.; Shibata I.; Baba A. Tetrahedron Lett. 2001, 42, 4661.
	(b) Rahm A.; Amardeil R.; Degueil-Castaing M. J. Organomet. Chem. 1989, 371, 4.
[50]	Yang J.; Brookhart M. Adv. Synth. Catal. 2009, 351, 175.
[51]	Krishnamurthy S.; Brown H. C. J. Org. Chem. 1980, 45, 849.
[52]	Krishnamurthy S.; Brown H. C. J. Org. Chem. 1982, 47, 276.
[53]	Xiao J.; Ma Y.; Wu X.; Gao J.; Tang Z.; Han L.-B. RSC Adv. 2019, 9, 22343.
[54]	(a) Eren G.; Ünlü S.; Nunez M.-T.; Labeaga L.; Ledo F.; Entrena A.; Banoglu E.; Costantino G.; Sahin M. F. Bioorg. Med. Chem. 2010, 18, 6367. pmid: 9544213
	(b) Xue N.; Zhou Y.; Wang G.; Miao W.; Qu J. J. Heterocycl. Chem. 2010, 47, 15. pmid: 9544213
	(c) Ucar H.; Derpoorten K.V.; Cacciaguerra S.; Spampinato S.; Stables J. P. J. Med. Chem. 1998, 41, 1138. pmid: 9544213
[55]	Noujima A.; Mitsudome T.; Mizugaki T.; Jitsukawa K.; Kaneda K. Green Chem. 2013, 15, 608.
[56]	Ram R. N.; Soni V. K. J. Org. Chem. 2013, 78, 11935. doi: 10.1021/jo401985h pmid: 24168289
[57]	Zhang W.; Li Q.; Shi T. CN 107188864, 2019.
[58]	Wang X.; Xiang J.; Wang J.; Yu Z.; Tang Z.-L.; Xiao J. Tetrahedron 2022, 127, 133094.
[59]	Li P.; Wischert R.; Métivier P. Angew. Chem., Int. Ed. 2017, 56, 15989.
[60]	Montchamp J.-L. Acc. Chem. Res. 2014, 47, 77.
[61]	Koshti V.; Gaikwad S.; Chikkali S. H. Coord. Chem. Rev. 2014, 265, 52.
[62]	Cheng R.; Li C.-J. Angew. Chem., Int. Ed. 2023, 62, e202301730.
[63]	Zhu J.; Ye Y.; Huang Y. Organometallics 2022, 41, 2342.
[64]	Wang Jie; Xiao J.; Tang Z.-L.; Lan D.-H.; Han L.-B. J. Org. Chem. 2024, 89, 5109.
[65]	(a) Atsumi S.; Hanai T.; Liao J. C. Nature 2008, 451, 86.
	(b) Ma S. K.; Gruber J.; Davis C.; Newman L.; Gray D.; Wang A.; Grate J.; Huisman G. W.; Sheldon R. A. Green Chem. 2010, 12, 81.
[66]	Tensi L.; Macchioni A. ACS Catal. 2020, 10, 7945.

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