Synlett, Inhaltsverzeichnis Synlett 2014; 25(08): 1089-1092DOI: 10.1055/s-0033-1340977 letter © Georg Thieme Verlag Stuttgart · New York A Concise Organocatalytic Route to Protected (2S,4R)-4-Hydroxyornithine and (+)-Pseudohygroline Vishwajeet Jha Organic Chemistry Division, CSIR-National Chemical Laboratory (CSIR-NCL), Homi Bhabha Road, Pune – 411008, India Fax: +91(20)25902629 eMail: pk.tripathi@ncl.res.in , Pradeep Kumar* Organic Chemistry Division, CSIR-National Chemical Laboratory (CSIR-NCL), Homi Bhabha Road, Pune – 411008, India Fax: +91(20)25902629 eMail: pk.tripathi@ncl.res.in › Institutsangaben Artikel empfehlen Abstract Artikel einzeln kaufen Alle Artikel dieser Rubrik Abstract A practical, efficient, and organocatalytic approach to the synthesis of (2S,4R)-4-hydroxyornithine and (+)-pseudohygroline is reported using proline-catalyzed sequential α-aminoxylation/α-amination reaction and Horner–Wadsworth–Emmons olefination reaction of an aldehyde as the key step. Key words Key wordsaldehydes - amination - amino alcohols - Wittig reaction - cyclization - enantioselectivity Volltext Referenzen References and Notes 1a Shibahara S, Kondo S, Maeda K, Umezawa H, Ohno M. J. Am. Chem. Soc. 1972; 94: 4353 1b Kozikowski AP, Chen Y.-Y. J. Org. Chem. 1981; 46: 5248 1c Wang Y.-F, Izawa T, Kobayashi S, Ohno M. J. Am. Chem. Soc. 1982; 104: 6465 1d Hashiguchi S, Kawada A, Natsugari H. J. Chem. Soc., Perkin Trans. 1 1991; 2435 1e Knapp S. Chem. Rev. 1995; 95: 1859 1f Sakai R, Kamiya H, Murata M, Shimamoto K. J. Am. Chem. Soc. 1997; 119: 4112 1g Haight AR, Stuk TL, Allen MS, Bhagavatula L, Fitzgerald M, Hannick SM, Kerdesky FA. J, Menzia JA, Parekh SI, Robbins TA, Scarpetti D, Tien J.-H. J. Org. Process Res. Dev. 1999; 3: 94 1h Sham HL, Zhao C, Li L, Betebenner DA, Saldivar A, Vasavanonda S, Kempf DJ, Plattner JJ, Norbeck DW. Bioorg. Med. Chem. Lett. 2002; 12: 3101 2 For excellent review on use of chiral 1,3-amino alcohol in asymmetric organic synthesis, see: Lait SM, Rankic DA, Keay BA. Chem. Rev. 2007; 107: 767 For recent synthesis of 1,3-amino alcohol, see 3a Yadav JS, Jayasudhan Reddy Y, Adi Narayana Reddy P, Subba Reddy BV. Org. Lett. 2013; 15: 546 3b Lee JS, Kim D, Lozano L, Kong SB, Han H. Org. Lett. 2013; 15: 554 ; and references cited therein 4a Sulser H, Stute R. Experientia 1976; 32: 422 4b Rozan P, Kuo Y.-H, Lambein F. Phytochemistry 2001; 58: 281 5a Bell EA, Tirimanna AS. L. Biochem. J. 1964; 356 5b Hatanaka S, Kaneko S, Saito K, Ishida Y. Phytochemistry 1981; 20: 2291 6 Denning DW. J. Antimicrob. Chemother. 1997; 40: 611 7 Kondo S, Meguriya N, Mogi H, Aota T, Miura K, Fujii T, Hayashi I, Makino K, Yamamoto M, Nakajima N. J. Antibiot. 1980; 33: 533 8a Pruess DL, Kellett M. J. Antibiot. 1983; 36: 208 8b Evans RH. Jr, Ax H, Jacoby A, Williams TH, Jenkis E, Scannell JP. J. Antibiot. 1983; 36: 213 8c Muller J.-C, Toome V, Pruess DL, Blount JF, Weigele M. J. Antibiot. 1983; 36: 217 8d Shiro Y, Kato K, Fujii M, Idab Y, Akitaa H. Tetrahedron 2006; 62: 8687 ; and references cited therein 9 Ezaki M, Iwami M, Yamashita M, Hashimoto S, Komori T, Umehara K, Mine Y, Kohsaka M, Aoki H, Imanaka I. J. Antibiot. 1985; 38: 1453 10a Lampe T, Adelt I, Beyer D, Brunner N, Endermann R, Ehlert K, Kroll H.-P, von Nussbaum F, Raddatz S, Rudolph J, Schiffer G, Schumacher A, Cancho-Grande Y, Michels M, Weigand S. WO 2003106480, 2003 ; Chem. Abstr. 2004, 140, 59934. 10b Lampe T, Adelt I, Beyer D, Brunner N, Endermann R, Ehlert K, Kroll H.-P, von Nussbaum F, Raddatz S, Rudolph J, Schiffer G, Schumacher A ; Chem. Abstr. 2004, 140, 164239. 11a Platonava TF. Kuzovkov A. D. 1963; 17: 19 11b Fitzgerald JS. Aust. J. Chem. 1965; 18: 589 11c Martin SA, Rovirosa J, Gambaro V, Castillo M. Phytochemistry 1980; 19: 2007 11d Pomilio AB, Gonzalez MD, Eceizabarren CS. Phytochemistry 1996; 41: 1393 12a Talbot G, Gaudry R, Berlinguet L. Can. J. Chem. 1956; 34: 911 12b Mizusaki K, Makisumi S. Bull. Chem. Soc. Jpn. 1981; 54: 470 12c Jackson RF. W, Wood A, Wythes MJ. Synlett 1990; 735 12d Häusler J. Liebigs Ann. Chem. 1992; 1231 12e Jackson RF. W, Rettie AB, Wood A, Wythes MJ. J. Chem. Soc., Perkin Trans. 1 1994; 1719 12f Girard A, Greck C, Genet JP. Tetrahedron Lett. 1998; 39: 4259 12g Mues H, Kazmaier U. Synthesis 2001; 487 12h Rudolph J, Hannig F, Theis H, Wischnat R. Org. Lett. 2001; 3: 3153 12i Lepine R, Carbonnelle A.-C, Zhu J. Synlett 2003; 1455 12j Paintner FF, Allmendinger L, Bauschke G, Klemann P. Org. Lett. 2005; 7: 1423 12k Pandey SK, Pandey M, Kumar P. Tetrahedron Lett. 2008; 49: 3297 13a Bhat C, Tilve SG. Tetrahedron Lett. 2011; 52: 6566 13b Yadav JS, Narasimhulu G, Reddy NM, Reddy BV. S. Tetrahedron Lett. 2010; 51: 1574 13c Davies SG, Fletcher AM, Roberts PM, Smith AD. Tetrahedron 2009; 65: 10192 13d Knight DW, Salter R. Tetrahedron Lett. 1999; 40: 5915 13e Louis C, Hootele C. Tetrahedron: Asymmetry 1997; 8: 109 13f Takahata H, Kubota M, Momose T. Tetrahedron: Asymmetry 1997; 8: 2801 13g Enierga G, Hockless DC. R, Perlmutter P, Rose M, Sjoberg S, Wong K. Tetrahedron Lett. 1998; 39: 2813 13h Murahashi S.-I, Imada Y, Kohno M, Kawakami T. Synlett 1993; 395 14a Dalko PL, Moisan L. Angew. Chem. Int. Ed. 2004; 43: 5138 14b Berkessel A, Gröger H. Asymmetric Organocatalysis: From Biomimetic Concepts to Applications in Asymmetric Synthesis. Wiley–VCH; Weinheim: 2005 14c Seayed J, List B. Org. Biomol. Chem. 2005; 3: 719 15 MacMillan DW. C. Nature (London) 2008; 455: 304 16 Jha V, Kondekar NB, Kumar P. Org. Lett. 2010; 12: 2762 17a Kumar P, Dwivedi N. Acc. Chem. Res. 2013; 46: 289 17b Kauloorkar SV, Jha V, Kumar P. RSC Adv. 2013; 3: 18288 17c Kumar P, Jha V, Gonnade RG. J. Org. Chem. 2013; 78: 11756 17d Jha V, Kumar P. RSC Adv. 2014; 4: 3238 18a Fernandes RA, Kumar P. Tetrahedron Lett. 2000; 41: 10309 18b Naidu SV, Kumar P. Tetrahedron Lett. 2003; 44: 1035 18c Kandula SV, Kumar P. Tetrahedron Lett. 2003; 44: 1957 18d Kondekar NB, Kandula SV, Kumar P. Tetrahedron Lett. 2004; 45: 5477 18e Pandey SK, Kandula SV, Kumar P. Tetrahedron Lett. 2004; 45: 5877 19a Zhong G. Angew. Chem. Int. Ed. 2003; 42: 4247 19b Chua PJ, Tan B, Zhong G. Green Chem. 2009; 11: 543 20a List B. J. Am. Chem. Soc. 2002; 124: 5656 20b Kotkar SP, Chavan VB, Sudalai A. Org. Lett. 2007; 9: 1001 21 The ee of 7a was determined by derivatizing it with Mosher’s acid and analyzing the 19F NMR spectrum. The ee of 7b was determined by comparing its specific rotation with the literature value.24a The diastereomeric ratios of 10 and 13 were determined using HPLC analysis (see Supporting Information). 22 Dibenzyl 1-{(2S,4R)-5-[(tert-Butoxycarbonyl)amino]-4-[(tert-butyldimethylsilyl)oxy]-1-hydroxypentan-2-yl}hydrazine-1,2-dicarboxylate (10) Colorless oil; yield 2.122 g (63%). [α]D 25 –9.56 (c 1.0, CHCl3). IR (CHCl3): νmax = 3019, 2956, 1712, 1505, 1216 cm–1. 1H NMR (200 MHz, CDCl3): δ = 0.00 (s, 3 H), 0.02 (s, 3 H), 0.90 (s, 9 H), 1.45 (s, 9 H), 1.66–1.82 (m, 2 H), 3.24–3.48 (m, 2 H), 3.90–4.15 (m, 3 H), 4.40–4.73 (m,1 H), 5.07–5.34 (m, 4 H), 6.11–6.19 (m, 1 H), 7.22–7.36 (m, 10 H) ppm. 13C NMR (50 MHz, CDCl3): δ = –4.8, –4.7, 17.9, 25.8, 28.6, 31.8, 32.6, 53.3, 62.3, 62.5, 67.9, 71.8, 71.9, 79.7, 126.4, 127.8, 128.1, 128.5, 129.3, 135.3, 135.5, 135.9, 138.1, 138.3, 155.9, 156.5, 158.1, 158.6 ppm. ESI-MS: m/z = 654.43 [M + Na]+. Anal. Calcd (%) for C32H49N3O8Si: C, 60.83; H, 7.82; N, 6.65. Found: C, 60.70; H, 7.91; N, 6.57. Dibenzyl 1-{(4S,6S,E)-6-[(tert-butyldimethylsilyl)oxy]-1-ethoxy-1-oxohept-2-en-4-yl}hydrazine-1,2-dicarboxylate (13) Colorless oil; yield 1.33 g (65%). [α]D 25 +2.32 (c 0.5, CHCl3). IR (CHCl3): νmax = 3295, 2956, 1755, 1719, 1406, 1043 cm–1. 1H NMR (200 MHz, CDCl3): δ = –0.02 (s, 3 H), 0.03 (s, 3 H), 0.85 (s, 9 H), 1.16 (d, J = 6.2 Hz, 3 H), 1.28 (t, J = 7.1 Hz, 2 H), 1.64–1.72 (m, 2 H), 3.76–3.93 (m, 1 H), 4.19 (q, J = 7.1 Hz, 2 H), 4.91–5.15 (m, 5 H), 5.94 (m, 1 H), 6.57 (br s, 1 H), 6.83 (dd, J = 6.8, 15.6 Hz, 1 H), 7.31 (m, 10 H) ppm. 13C NMR (50 MHz, CDCl3): δ = –4.8, –4.1, 14.1, 17.9, 24.1, 29.9, 40.6, 56.5, 60.5, 67.4, 67.7, 68.3, 122.9, 128.0, 128.1, 128.3, 128.4, 135.5, 144.6, 155.3, 156.3, 166.1 ppm. ESI-MS: m/z = 607.32 [M + Na]+. Anal. Calcd (%) for C31H44N2O7Si: C, 63.67; H, 7.58; N, 4.79. Found: C, 63.39; H, 7.43; N, 4.92. 23 (2S,4R)-2,5-Bis{(tert-butoxycarbonyl)amino)-4-[(tert-butyldimethylsilyl]oxy}pentanoic Acid (12) Viscous oil; yield 42 mg (82%). [α]D 25 –34.56 (c 1, CHCl3). IR (CHCl3): νmax = 3346, 2910, 1716, 1453 cm–1. 1H NMR (200 MHz, CDCl3): δ = 0.08 (s, 6 H), 0.88 (s, 9 H), 1.45 (s, 18 H), 1.73–1.79 (m, 2 H), 3.07–3.28 (m, 1 H), 3.55–3.80 (m, 1 H), 3.90–4.11 (m, 2 H), 5.59 (br s, 1 H), 5.74 (br s, 1 H) ppm. 13C NMR (50 MHz, CDCl3): δ = –5.1, –4.7, 14.1, 18.0, 22.7, 28.3, 31.9, 42.5, 65.2, 66.4, 80.4, 163.3 ppm. ESI-MS: m/z = 485.21 [M + Na]+. Anal. Calcd (%) for C21H42N2O7Si: C, 54.52; H, 9.15; N, 6.05. Found: C, 54.25; H, 9.37; N, 5.75. (+)-Pseudohygroline (5a) Colorless liquid; yield 0.02 g (95%). [α]D 25 –48.12 (c 0.5, EtOH). 1H NMR (200 MHz, CDCl3): δ = 1.17 (d, J = 6.2 Hz, 3 H), 1.31–1.45 (m, 3 H), 1.71–1.78 (m, 2 H), 1.98–2.04 (m, 1 H), 2.31–2.40 (m, 1 H), 2.37 (s, 3 H), 2.69–2.77 (m, 1 H), 3.00–3.08 (m, 1 H), 3.87–3.96 (m, 1 H) ppm. 13C NMR (50 MHz, CDCl3): δ = 21.9, 22.8, 29.1, 38.1, 40.6, 56.5, 67.1, 68.2 ppm. ESI-MS: m/z = 144.22 [M + H]+. 24a Jacobs H, Berryman K, Jones J, Gopalan A. Synth. Commun. 1990; 20: 999 24b Reddy CR, Srikanth B, Dilipkumar U, Rao KV. M, Jagadeesh B. Eur. J. Org. Chem. 2013; 525 Zusatzmaterial Zusatzmaterial Supporting Information
