Practical Preparation
Methods for Highly Active Azaadamantane-Nitroxyl-Radical-Type Oxidation
Catalysts

Masatoshi Shibuya; Yusuke Sasano; Masaki Tomizawa; Toshimasa Hamada; Masami Kozawa; Noriaki Nagahama; Yoshiharu Iwabuchi

doi:10.1055/s-0030-1260257

FEATUREARTICLE

Practical Preparation Methods for Highly Active Azaadamantane-Nitroxyl-Radical-Type Oxidation Catalysts

Masatoshi Shibuya^a, Yusuke Sasano^a, Masaki Tomizawa^a, Toshimasa Hamada^b, Masami Kozawa^c, Noriaki Nagahama^c, Yoshiharu Iwabuchi*^a
^a Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aobayama, Sendai 980-8578, Japan
Fax: +81(22)7956845; e-Mail: iwabuchi@mail.pharm.tohoku.ac.jp;
^b Performance Materials Division, Planning & Development Dept., Nissan Chemical Industries, Ltd., 3-7-1 Kanda-Nishiki-cho, Chiyoda-ku, Tokyo 101-0054, Japan
^c Synthesis Research Dept., Nissan Chemical Industries, Ltd., 2-10-1 Tsuboi-nishi, Funabashi, Chiba 274-8507, Japan

Abstract

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Abstract

We have recently disclosed that a less hindered class of nitroxyl radicals, i.e., 2-azaadamantan-N-oxyl (AZADO), 1-Me-AZADO, and 9-azabicyclo[3.3.1]nonan-N-oxyl (ABNO), exhibit marked catalytic activity for the oxidation of alcohols with the aid of environmentally friendly oxidants, offering a green and sustainable option for current alcohol oxidation. Encouraged by their outstanding catalytic performance, we envisioned the development of scalable routes to these radicals that could be extended to the commercialization of these radicals for benchtop use as well as for industrial use as optional reagents that complement TEMPO, the flagship compound of stable nitroxyl radicals. We herein describe short and reproducible preparation methods for AZADO and 1-Me-AZADO, featuring an efficient construction of the 2-azaadamantane skeleton.

1 Introduction

2 1-Me-AZADO and AZADO: First-Generation Syntheses

3 Second-Generation Synthesis of 1-Me-AZADO

4 Synthetic Venture towards 2-Azaadamantane: Second-Generation Synthesis of AZADO

5 Conclusion

Key words

alcohol oxidation - organocatalyst - nitroxyl radical - adamantane - hydroamination

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References

<A NAME="RF76611SS-1A">1a</A> Bäckvall J.-E. Modern Oxidation Methods Wiley-VCH; Weinheim: 2004.

<A NAME="RF76611SS-1B">1b</A> Ley SV. In Comprehensive Organic Synthesis Vol. 7: Trost BM. Fleming I. Pergamon; Oxford: 1991. p.251-327

<A NAME="RF76611SS-2A">2a</A> Studer A. Tebben L. Angew. Chem. Int. Ed. 2011, 50: 5034

<A NAME="RF76611SS-2B">2b</A> Ciriminna R. Pagliaro M. Org. Process Res. Dev. 2010, 14: 245

<A NAME="RF76611SS-2C">2c</A> Vogler T. Studer A. Synthesis 2008, 1979

<A NAME="RF76611SS-2D">2d</A> Sheldon RA. Arends IWCE. Adv. Synth. Catal. 2004, 346: 1051

<A NAME="RF76611SS-2E">2e</A> Adam W. Saha-Moller CR. Ganeshpure PA. Chem. Rev. 2001, 101: 3499

<A NAME="RF76611SS-2F">2f</A> deNooy AEJ. Besemer AC. vanBekkum H. Synthesis 1996, 1153

<A NAME="RF76611SS-2G">2g</A> Bobbitt JM. Flores MCL. Heterocycles 1988, 27: 509

<A NAME="RF76611SS-3A">3a</A> Anelli PL. Banfi S. Montanari F. Quici S. J. Org. Chem. 1989, 54: 2970

<A NAME="RF76611SS-3B">3b</A> Anelli PL. Biffi C. Montanari F. Quici S. J. Org. Chem. 1987, 52: 2559

<A NAME="RF76611SS-4">4</A> DeMico A. Margarita R. Parlanti L. Vescovi A. Piancatelli G. J. Org. Chem. 1997, 62: 6974

<A NAME="RF76611SS-5A">5a</A> Miller RA. Hoerrner RS. Org. Lett. 2003, 5: 285

<A NAME="RF76611SS-5B">5b</A> De Luca L. Giacomelli G. Masala S. Porcheddu A. J. Org. Chem. 2003, 68: 4999

<A NAME="RF76611SS-5C">5c</A> Bragd PL. Besemer AC. van Bekkum H. Carbohydr. Polym. 2002, 49: 397

<A NAME="RF76611SS-5D">5d</A> De Luca L. Giacomelli G. Porcheddu A. Org. Lett. 2001, 3: 3041

<A NAME="RF76611SS-5E">5e</A> Bolm C. Magnus AS. Hildebrand JP. Org. Lett. 2000, 2: 1173

<A NAME="RF76611SS-5F">5f</A> Rychnovsky SD. Vaidyanathan R. J. Org. Chem. 1999, 64: 310

<A NAME="RF76611SS-5G">5g</A> Cella JA. Mcgrath JP. Kelley JA. Elsoukkary O. Hilpert L. J. Org. Chem. 1977, 42: 2077

<A NAME="RF76611SS-6A">6a</A> Zhao MM. Li J. Mano E. Song ZJ. Tschaen DM. Org. Synth. 2005, 81: 195

<A NAME="RF76611SS-6B">6b</A> Zanka A. Chem. Pharm. Bull. 2003, 51: 888

<A NAME="RF76611SS-6C">6c</A> Zhao MZ. Li J. Mano E. Song ZG. Tschaen DM. Grabowski EJJ. Reider PJ.
J. Org. Chem. 1999, 64: 2564

<A NAME="RF76611SS-6D">6d</A> Epp JB. Widlanski TS. J. Org. Chem. 1999, 64: 293

<A NAME="RF76611SS-7A">7a</A> Caron S. Dugger RW. Ruggeri SG. Ragan JA. Ripin DHB. Chem. Rev. 2006, 106: 2943

<A NAME="RF76611SS-7B">7b</A> Dugger RW. Ragan JA. Ripin DHB. Org. Process Res. Dev. 2005, 9: 253

<A NAME="RF76611SS-8A">8a</A> Hansen TM. Florence GJ. Lugo-Mas P. Chen JH. Abrams JN. Forsyth CJ. Tetrahedron Lett. 2003, 44: 57

<A NAME="RF76611SS-8B">8b</A> Davis NJ. Flitsch SL. Tetrahedron Lett. 1993, 34: 1181

<A NAME="RF76611SS-8C">8c</A> Siedlecka R. Skarzewski J. Mlochowski J. Tetrahedron Lett. 1990, 31: 2177

<A NAME="RF76611SS-8D">8d</A> Semmelhack MF. Chou CS. Cortes DA. J. Am. Chem. Soc. 1983, 105: 4492

<A NAME="RF76611SS-9A">9a</A> Adamic K. Bowman DF. Gillan T. Ingold KU. J. Am. Chem. Soc. 1971, 93: 902

<A NAME="RF76611SS-9B">9b</A> Mendenha Gd. Ingold KU. J. Am. Chem. Soc. 1972, 94: 7166

<A NAME="RF76611SS-10A">10a</A> Malatest V. Ingold KU. J. Am. Chem. Soc. 1973, 95: 6404

<A NAME="RF76611SS-10B">10b</A> Mendenha Gd. Ingold KU. J. Am. Chem. Soc. 1973, 95: 6395

<A NAME="RF76611SS-10C">10c</A> Shibuya M. Tomizawa M. Sasano Y. Iwabuchi Y. J. Org. Chem. 2009, 74: 4619

<A NAME="RF76611SS-11A">11a</A> Dupeyre RM. Rassat A. Tetrahedron Lett. 1975, 16: 1839

<A NAME="RF76611SS-11B">11b</A> Dupeyre RM. Rassat A. Tetrahedron 1978, 34: 1501

<A NAME="RF76611SS-12A">12a</A> Henkel JG. Faith WC. J. Org. Chem. 1981, 46: 4953

<A NAME="RF76611SS-12B">12b</A> Stetter H. Tacke P. Gartner J. Chem. Ber. 1964, 97: 3480

<A NAME="RF76611SS-13A">13a</A> Muraoka O. Wang YL. Okumura M. Nishiura S. Tanabe G. Momose T. Synth. Commun. 1996, 26: 1555

<A NAME="RF76611SS-13B">13b</A> Shibuya M. Taniguchi T. Takahashi M. Ogasawara K. Tetrahedron Lett. 2002, 43: 4145

<A NAME="RF76611SS-14">14</A> Ipaktschi J. Chem. Ber. 1984, 117: 856

<A NAME="RF76611SS-15">15</A> Shibuya M. Tomizawa M. Suzuki I. Iwabuchi Y. J. Am. Chem. Soc. 2006, 128: 8412

<A NAME="RF76611SS-16A">16a</A> Tomizawa M. Shibuya M. Iwabuchi Y. Org. Lett. 2009, 11: 1829

<A NAME="RF76611SS-16B">16b</A> Shibuya M. Sato T. Tomizawa M. Iwabuchi Y. Chem. Commun. 2009, 1739

<A NAME="RF76611SS-17">17</A> Stetter H. Gartner J. Tacke P. Chem. Ber. 1966, 99: 1435

<A NAME="RF76611SS-18A">18a</A> Staas WH. Spurlock LA. J. Org. Chem. 1974, 39: 3822

<A NAME="RF76611SS-18B">18b</A> Sasaki T. Eguchi S. Toru T. J. Org. Chem. 1970, 35: 4109

<A NAME="RF76611SS-19A">19a</A> Hane JT. Henkel JG. Tetrahedron Lett. 1990, 31: 2949

<A NAME="RF76611SS-19B">19b</A> Sasaki T. Eguchi S. Okano T. Wakata Y. J. Org. Chem. 1983, 48: 4067

<A NAME="RF76611SS-19C">19c</A> Sasaki T. Eguchi S. Okano T. Tetrahedron Lett. 1982, 23: 4969

<A NAME="RF76611SS-20A">20a</A> Tius MA. Dixon DD. Sethumadhavan D. Benneche T. Banaag AR. Thakur GA. Bowman A. Wood JT. Makriyannis A. J. Med. Chem. 2010, 53: 5656

<A NAME="RF76611SS-20B">20b</A> Tius MA. Le Goanvic D. J. Org. Chem. 2006, 71: 7800

<A NAME="RF76611SS-20C">20c</A> Nirogi R, Mohammed AR, Ahmad I, Jayarajan P, Kandikere NV, Shinde AK, Kambhampati RS, Bhyrapuneni G, Ravula J, Patanala SM, and Jasti V. inventors; WO 2011,030,349.

<A NAME="RF76611SS-21A">21a</A> Shioiri T. Murata M. Hamada Y. Chem. Pharm. Bull. 1987, 35: 2698

<A NAME="RF76611SS-21B">21b</A> Murato K. Shioiri T. Yamada SI. Chem. Pharm. Bull. 1975, 23: 1738

<A NAME="RF76611SS-21C">21c</A> Ninomiya K. Shioiri T. Yamada S. Tetrahedron 1974, 30: 2151

<A NAME="RF76611SS-22">22</A> Hamada T, Nagahama N, Kozawa M, Iwabuchi Y, Shibuya M, Tomizawa M, and Sasano Y. inventors; WO 2009,066,735.