Phosphorodiamidic Acid as a Novel Structural Motif of Brønsted Acid Catalysts for Direct Mannich Reaction of N-Acyl Imines with 1,3-Dicarbonyl Compounds

Abstract

Phosphorodiamidic acid 1 was developed as an efficient Brønsted acid catalyst for the direct Mannich reaction of N-acyl imines with 1,3-dicarbonyl compounds. Phosphorodiamidic acids were proposed as a novel structural motif of enantioselective ­Brønsted acid catalysts because they possess unique features, including the capability of introducing various substituents to the nitrogen atoms and the preparation from readily available chiral diamines in a short step. We demonstrated that chiral phosphorodiamidic acid 1b derived from binaphthalene bis(sulfonamide) functioned as an enantioselective catalyst to give the Mannich product in an optically active form.

organocatalyst - Mannich reaction - green chemistry - asymmetric catalysis - imines

References and Notes

<A NAME="RY07505ST-1">1</A>

Present address: Sagami Chemical Research Center, Ayase 252-1193, Japan.

Reviews on atom economy:

<A NAME="RY07505ST-2A">2a</A> Trost BM. Science  1991,  254:  1471 

<A NAME="RY07505ST-2B">2b</A> Trost BM. Angew. Chem., Int. Ed. Engl.  1995,  34:  259 

<A NAME="RY07505ST-2C">2c</A> Trost BM. Acc. Chem. Res.  2002,  35:  695 

Recent reviews on organocatalysis:

<A NAME="RY07505ST-3A">3a</A> Dalko PL. Moisan L. Angew. Chem. Int. Ed.  2004,  43:  5138 

<A NAME="RY07505ST-3B">3b</A>

Special issue on ‘Organic Catalysis’: Adv. Synth. Catal. 2004, 346.

<A NAME="RY07505ST-3C">3c</A>

Special issue on ‘Enantioselective Organocatalysis’: Acc. Chem. Res. 2004, 37.

<A NAME="RY07505ST-3D">3d</A> Berkessel A. Gröger H. Asymmetric Organocatalysis - From Biomimetic Concepts to Powerful Methods for Asymmetric Synthesis   Wiley-VCH; Weinheim: 2005. 

<A NAME="RY07505ST-3E">3e</A> Seayad J. List B. Org. Biomol. Chem.  2005,  3:  719 

<A NAME="RY07505ST-3F">3f</A> Hayashi Y. J. Synth. Org. Chem. Jpn.  2005,  63:  464 

For reviews on Brønsted acid catalysis, see:

<A NAME="RY07505ST-4A">4a</A> Schreiner PR. Chem. Soc. Rev.  2003,  32:  289 

<A NAME="RY07505ST-4B">4b</A> Pihko PM. Angew. Chem. Int. Ed.  2004,  43:  2062 

For selected recent examples of asymmetric Brønsted acid catalysis, see:

<A NAME="RY07505ST-5A">5a</A> Huang Y. Unni AK. Thadani AN. Rawal VH. Nature (London)  2003,  424:  146 

<A NAME="RY07505ST-5B">5b</A> Joly GD. Jacobsen EN. J. Am. Chem. Soc.  2004,  126:  4102 

<A NAME="RY07505ST-5C">5c</A> Thadani AN. Stankovic AR. Rawal VH. Proc. Natl. Acad. Sci. U.S.A.  2004,  101:  5846 

<A NAME="RY07505ST-5D">5d</A> Du H. Zhao D. Ding K. Chem.-Eur. J.  2004,  10:  5964 

<A NAME="RY07505ST-5E">5e</A> Momiyama N. Yamamoto H. J. Am. Chem. Soc.  2005,  127:  1080 

<A NAME="RY07505ST-5F">5f</A> Unni AK. Takenaka N. Yamamoto H. Rawal VH. J. Am. Chem. Soc.  2005,  127:  1336 

<A NAME="RY07505ST-5G">5g</A> Fuerst DE. Jacobsen EN. J. Am. Chem. Soc.  2005,  127:  8964 

<A NAME="RY07505ST-5H">5h</A> Rueping M. Sugiono E. Azap C. Theissmann T. Bolte M. Org. Lett.  2005,  7:  3781 

<A NAME="RY07505ST-5I">5i</A> Zhuang W. Hazell RG. Jørgensen KA. Org. Biomol. Chem.  2005,  3:  2566 

<A NAME="RY07505ST-5J">5j</A> Zhuang W. Poulsen TB. Jørgensen KA. Org. Biomol. Chem.  2005,  3:  3284 

<A NAME="RY07505ST-5K">5k</A> Tonoi T. Mikami K. Tetrahedron Lett.  2005,  46:  6355 

<A NAME="RY07505ST-5L">5l</A> Herrera RP. Sgarzani V. Bernardi L. Ricci A. Angew. Chem. Int. Ed.  2005,  44:  6576 

<A NAME="RY07505ST-6A">6a</A> Lewis Acid Reagents: A Practical Approach   Yamamoto H. Oxford University Press; Oxford: 1999. 

<A NAME="RY07505ST-6B">6b</A> Lewis Acids in Organic Synthesis   Yamamoto H. Wiley-VCH; Weinheim: 2000. 

<A NAME="RY07505ST-7A">7a</A> Akiyama T. Itoh J. Yokota K. Fuchibe K. Angew. Chem. Int. Ed.  2004,  43:  1566 

<A NAME="RY07505ST-7B">7b</A> Akiyama T. Morita H. Itoh J. Fuchibe K. Org. Lett.  2005,  7:  2583 

<A NAME="RY07505ST-8A">8a</A> Uraguchi D. Terada M. J. Am. Chem. Soc.  2004,  126:  5356 

<A NAME="RY07505ST-8B">8b</A> Uraguchi D. Sorimachi K. Terada M. J. Am. Chem. Soc.  2004,  126:  11804 

<A NAME="RY07505ST-8C">8c</A> Uraguchi D. Sorimachi K. Terada M. J. Am. Chem. Soc.  2005,  127:  9630 

For stereoselective direct Mannich reaction catalyzed by achiral Brønsted acid, see:

<A NAME="RY07505ST-9A">9a</A> Wu Y.-S. Cai J. Hu Z.-Y. Lin G.-X. Tetrahedron Lett.  2004,  45:  8949 

<A NAME="RY07505ST-9B">9b</A> Akiyama T. Matsuda K. Fuchibe K. Synlett  2005,  322 

<A NAME="RY07505ST-10A">10a</A> Review: Lucet D. Le Gall T. Mioskowski C. Angew. Chem. Int. Ed.  1998,  37:  2581 ; and references therein

<A NAME="RY07505ST-10B">10b</A> Corey EJ. Imwinkelried R. Pikul S. Xiang YB. J. Am. Chem. Soc.  1989,  111:  5493 

<A NAME="RY07505ST-10C">10c</A> Corey EJ. Yu C.-M. Kim SS. J. Am. Chem. Soc.  1989,  111:  5495 

<A NAME="RY07505ST-11">11</A>

Preparation of Phosphorodiamidic Acid ( 1a).
N,N′-Ditosylbenzene-1,2-diamine (208.3 mg, 0.5 mmol), prepared according to the literature procedure, [23] was dissolved into pyridine (1 mL) under nitrogen atmosphere. To the resulting solution was added phosphorus oxychloride (115.0 mg, 0.75 mmol) at r.t. After being stirred for 12 h at ambient temperature, H₂O (1 mL) was poured into the reaction mixture. The resulting suspension was stirred for additional 30 min. Then, EtOAc was added and all pyridine was removed by reverse extraction with 1 N HCl. The organic phase was dried over Na₂SO₄. After being concentrated, the residue was purified by column chromatography. Compound 1a was isolated as a white solid in 90% yield. ¹H NMR (270 MHz, DMSO-d ₆,): δ = 2.30 (6 H, s), 6.79-6.86 (2 H, m), 7.17-7.24 (2 H, m), 7.31 (4 H, d, J = 8.4 Hz), 8.02 (4 H, d, J = 8.4 Hz). ¹³C NMR (67.8 MHz, DMSO-d ₆): δ = 21.0, 113.1 (d, J _P-C = 5.4 Hz), 122.9, 126.8 (t, J _P-C = 10.3 Hz), 127.9, 129.5, 135.7, 144.2. IR (KBr): 3425, 3072, 1375, 1175, 1119 cm^-1. HRMS (ESI): m/z calcd for C₂₀H₁₉N₂O₆PS₂ [M - H]^-: 477.0349. Found: 477.0351.

<A NAME="RY07505ST-12A">12a</A> For an excellent review of organocatalytic asymmetric direct Mannich reactions, see: Córdova A. Acc. Chem. Res.  2004,  37:  102 

See also:

<A NAME="RY07505ST-12B">12b</A> Poulsen TB. Alemparte C. Saaby S. Bella M. Jørgensen KA. Angew. Chem. Int. Ed.  2005,  44:  2896 

<A NAME="RY07505ST-12C">12c</A>

See ref. 3d, Chapter 5.2.

For metal complex-mediated asymmetric direct Mannich reactions, see:

<A NAME="RY07505ST-13A">13a</A> Juhl K. Gathergood N. Jørgensen KA. Angew. Chem. Int. Ed.  2001,  40:  2995 

<A NAME="RY07505ST-13B">13b</A> Trost BM. Terrell LR. J. Am. Chem. Soc.  2003,  125:  338 

<A NAME="RY07505ST-13C">13c</A> Matsunaga S. Kumagai N. Harada S. Shibasaki M. J. Am. Chem. Soc.  2003,  125:  4712 

<A NAME="RY07505ST-13D">13d</A> Bernardi L. Gothelf AS. Hazell RG. Jørgensen KA. J. Org. Chem.  2003,  68:  2583 

<A NAME="RY07505ST-13E">13e</A> Marigo M. Kjærsgaard A. Juhl K. Gathergood N. Jørgensen KA. Chem.-Eur. J.  2003,  9:  2359 

<A NAME="RY07505ST-13F">13f</A> Matsunaga S. Yoshida T. Morimoto H. Kumagai N. Shibasaki M. J. Am. Chem. Soc.  2004,  126:  8777 

<A NAME="RY07505ST-13G">13g</A> Hamashima Y. Sasamoto N. Hotta D. Somei H. Umebayashi N. Sodeoka M. Angew. Chem. Int. Ed.  2005,  44:  1525 

<A NAME="RY07505ST-13H">13h</A> Yoshida T. Morimoto H. Kumagai N. Matsunaga S. Shibasaki M. Angew. Chem. Int. Ed.  2005,  44:  3470 

<A NAME="RY07505ST-13I">13i</A> Kjærsgaard A. Jørgensen KA. Org. Biomol. Chem.  2005,  3:  804 

<A NAME="RY07505ST-13J">13j</A> Kundsen KR. Jørgensen KA. Org. Biomol. Chem.  2005,  3:  1362 

<A NAME="RY07505ST-14">14</A> Greene TW. Wuts PGM. Protective Groups in Organic Synthesis   3rd ed.:  John Wiley and Sons, Inc.; New York: 1999.  p.494-653  

<A NAME="RY07505ST-15">15</A> Nakamura Y. Matsubara R. Kobayashi S. Org. Lett.  2003,  5:  2481 

<A NAME="RY07505ST-16">16</A>

The distribution of keto-enol tautomers of 3 in CDCl₃ was measured by ¹H NMR. The percentages of the enol form are listed as follows: 3a: 72%; 3b: 61%; 3c: >98%; 3d: 6%; 3e: 6%; 3f: 21%; 3g: <2%.

<A NAME="RY07505ST-17">17</A>

Although in the case of unsymmetrical 1,3-dicarbonyl compounds, keto esters 3d,e and keto amide 3f, the diastereomeric mixtures were obtained, their ratios were changed during the course of experiment.

For binaphthalene bis(sulfonamide) derivatives as a chiral ligand for metal-based catalysts, see:

<A NAME="RY07505ST-18A">18a</A> Terada M. Motoyama Y. Mikami K. Tetrahedron Lett.  1994,  35:  6693 

<A NAME="RY07505ST-18B">18b</A> Mikami K. Motoyama Y. Terada M. Inorg. Chim. Acta  1994,  222:  71 

<A NAME="RY07505ST-18C">18c</A> Denmark SE. Christenson BL. O’Connor SP. Tetrahedron Lett.  1995,  36:  2219 

<A NAME="RY07505ST-18D">18d</A> Shi M. Sui W.-S. Chirality  2000,  12:  574 

<A NAME="RY07505ST-18E">18e</A> Ooi T. Saito A. Maruoka K. J. Am. Chem. Soc.  2003,  125:  3220 

<A NAME="RY07505ST-18F">18f</A> Yus M. Ramon DJ. Prieto O. Tetrahedron: Asymmetry  2003,  14:  1103 

<A NAME="RY07505ST-18G">18g</A> Ooi T. Ohmatsu K. Uraguchi D. Maruoka K. Tetrahedron Lett.  2004,  45:  4481 

<A NAME="RY07505ST-18H">18h</A> Akiyama K. Mikami K. Tetrahedron Lett.  2004,  45:  7217 

For binaphthalene-derived diazaphosphepines as a chiral ligand for metal-based catalysts, see:

<A NAME="RY07505ST-19A">19a</A> Reetz MT. Oka H. Goddard R. Synthesis  2003,  1809 

<A NAME="RY07505ST-19B">19b</A> Denmark SE. Fan Y. J. Am. Chem. Soc.  2003,  125:  7825 

<A NAME="RY07505ST-19C">19c</A> Monti C. Gennari C. Steele RM. Piarulli U. Eur. J. Org. Chem.  2004,  3557 

<A NAME="RY07505ST-19D">19d</A> Denmark SE. Beutner GL. Wynn T. Eastgate MD. J. Am. Chem. Soc.  2005,  127:  3774 

<A NAME="RY07505ST-20">20</A>

Compound (R)-1b: [α]_D 150 (c 0.99, CHCl₃). ¹H NMR (270 MHz, DMSO-d ₆): δ = 3.33 (6 H, s), 6.23 (4 H, d, J = 8.1 Hz), 6.74 (2 H, d, J = 7.6 Hz), 7.01 (4 H, d, J = 8.1 Hz), 7.10 (2 H, t, J = 7.6 Hz), 7.37 (2 H, t, J = 7.6 Hz), 7.43 (2 H, d, J = 7.6 Hz), 7.73 (2 H, d, J = 7.6 Hz), 7.75 (2 H, d, J = 7.6 Hz). ¹³C NMR (67.8 MHz, DMSO-d ₆): δ = 20.9, 125.3, 125.4, 125.8, 127.1, 127.4 (d, J _P-C = 1.0 Hz), 127.8, 128.1 (t, J _P-C = 1.5 Hz), 130.8 (t, J _P-C = 1.5 Hz), 131.1 (d, J _P-C = 1.0 Hz), 131.5 (d, J _P-C = 1.0 Hz), 132.1, 134.5-134.6 (m), 137.6-137.8 (m), 140.6 (d, J _P-C = 4.9 Hz). IR (KBr): 3458, 3055, 2910, 1344, 1171, 1113 cm^-1. HRMS (ESI): m/z calcd for C₃₄H₂₇N₂O₆PS₂ [M - H]^-: 653.0975. Found 653.0975.

<A NAME="RY07505ST-21">21</A>

Compound 4e: white solid; R _f = 0.20 (hexane-EtOAc, 2:1). HPLC analysis Chiralpak AD-H (hexane-EtOH, 80:20, 1.0 mL/min, 254 nm, 10 °C) 19.1 (S), 27.3 (R) min. ¹H NMR (270 MHz, CDCl₃): δ = 2.12 (3 H, s), 2.32 (3 H, s), 4.41 (1 H, d, J = 4.9 Hz), 6.06 (1 H, dd, J = 9.2, 4.9 Hz), 7.22-7.54 (8 H, m), 7.77-7.86 (2 H, m), 7.97 (1 H, br d, J = 9.2 Hz). ¹³C NMR (67.8 MHz, CDCl₃): δ = 29.8, 31.6, 52.3, 70.0, 126.3, 127.1, 127.8, 128.6, 128.8, 131.8, 133.7, 139.2, 166.8, 202.6, 205.9. IR (KBr): 3369, 3032, 2918, 1724, 1639, 1522 cm^-1. HRMS (ESI): m/z calcd for C₁₉H₁₉NaNO₃ [M + Na]⁺: 332.1257. Found: 332.1260.

<A NAME="RY07505ST-22">22</A>

The absolute configuration of Bz-product 4e was determined after transformation into the stereochemically known N-benzoylphenylglycine methyl ester. The stereochemical determination of 4a and the experimental procedure for derivatization of 4 to N-protected glycine methyl ester were described in ref. 8a.

<A NAME="RY07505ST-23">23</A> Dubey PK. Kulkarni SM. Kumar RV. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem.  2002,  41:  1305