Synthesis, Table of Contents Synthesis 2024; 56(05): 871-877DOI: 10.1055/a-2211-2343 paper Stereodivergent Synthesis of rac-cis- and rac-trans-4-Hydroxyphosphopipecolic Acids Authors Author Affiliations Juan Carlos Morales-Solís a Centro de Investigaciones Químicas-IICBA, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, Cuernavaca, Morelos 62209, Mexico Mario Ordóñez ∗ a Centro de Investigaciones Químicas-IICBA, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, Cuernavaca, Morelos 62209, Mexico Rubén Oswaldo Argüello-Velasco b Facultad de Ciencias Químicas e Ingeniería, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, Cuernavaca, Morelos 62209, Mexico José Luis Viveros-Ceballos a Centro de Investigaciones Químicas-IICBA, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, Cuernavaca, Morelos 62209, Mexico Victoria Labastida-Galván a Centro de Investigaciones Químicas-IICBA, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, Cuernavaca, Morelos 62209, Mexico Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) Abstract We report herein the first stereodivergent synthesis of rac-cis- and rac-trans-4-hydroxyphosphopipecolic acids. The main feature of this methodology is the controlled cis or trans reduction of 4-oxophosphopipecolates by exclusively varying the size of the hydride reagents. Thus, a small hydride reagent (NaBH4) adds selectively from the axial side of the carbonyl group to give the equatorial hydroxyl group (cis-product), whereas a bulky hydride reagent such as LiBH(sec-Bu)3 (L-Selectride®) preferentially attacks from the equatorial side, giving the hydroxyl group in the axial position (trans-product). In the last step, hydrolysis of the diethyl phosphonate and ethyl phenylphosphinate groups with bromotrimethylsilane, followed by methanolysis, led to the target compounds. Key words Key wordsstereodivergent synthesis - diastereoselective reduction - 4-hydroxyphosphopipecolic acid - heterocyclic α-aminophosphonic acids - heterocyclic α-aminophenylphosphinic acids Full Text References References 1a Purkayastha N, Haufe G. Synlett 2010; 1501 1b Sabat M, Johnson CR. Tetrahedron Lett. 2001; 42: 1209 1c Barluenga J, Aznar F, Valdés C, Ribas C. J. Org. Chem. 1998; 63: 3918 2a Szatmári I, Kiss L, Fülöp F. J. Heterocycl. Chem. 2006; 43: 1387 2b Skiles JW, Giannousis PP, Fales KR. Bioorg. Med. Chem. Lett. 1996; 6: 963 2c Ornstein PL, Schoepp DD, Arnold MB, Leander JD, Lodge D, Paschal JW, Elzey T. J. Med. Chem. 1991; 34: 90 3 Mukhtar TA, Wright GD. Chem. Rev. 2005; 105: 529 4 Parsy CC, Alexandre F.-R, Bidau V, Bonnaterre F, Brandt G, Caillet C, Cappelle S, Chaves D, Convard T, Derock M, Gloux D, Griffon Y, Lallos LB, Leroy F, Liuzzi M, Loi A.-G, Moulat L, Chiara M, Rahali H, Roques V, Rosinovsky E, Savin S, Seifer M, Standring D, Surleraux D. Bioorg. Med. Chem. 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