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Aldrichimica Acta 48.3 VOL. 48, NO. 3 • 2015 Ynamides: Powerful and Versatile Reagents for Chemical Synthesis Cyclic Sulfamidate Enabled Syntheses of Amino Acids, Peptides, Carbohydrates, and Natural Products Spiral into 3D with spirocyclic building blocks O N Boc S N S O O O O Spirocyclic modules containing four-membered rings 797154 are currently of growing interest to discovery chemists. Spirocyclic molecule Aldrich offers a suite of spirocyclic building blocks and starting materials in collaboration with Professor Dr. Erick Carreira. The use of these products allows Starting Materials Spirocyclic Building Blocks the synthesis of spirocycles with spatially well-defined exit vectors to creatively exploit three dimensions. In addition, spirocyclic building blocks provide access O O O CH3 Ts N to improved physicochemical properties through O N N Boc functionalization, innovative scaffolds in medicinal O N chemistry, and a useful collection of unprecedented Boc HO inputs for fragment-based libraries. 792586 795895 797502 O H2N N Boc Boc N O O O 797464 797545 N Ts O O O 793868 S N Boc N Boc O HO Professor Dr. Erick Carreira 797456 797561 References: (1) Burkhard, J. A.; Guérot, C.; Knust, H.; Carreira, E. M. Org. Lett. 2012, 14, 66. Venture farther into 3D and learn more: (2) Li, D. B.; Rogers-Evans, M.; Carreira, E. M. Org. Lett. 2013, 15, 4766. (3) Li, D. B.; Rogers-Evans, M.; Carreira, E. M. Org. Lett. 2011, 13, 6134. Aldrich.com/spirocycles (4) Carreira, E. M.; Fessard, T. C. Chem. Rev. 2014, 114, 8257. 84031-a 57 VOL. 48, NO. 3 • 2015 Aldrich Chemical Co. LLC. “PLEASE BOTHER US.” 6000 N. Teutonia Ave. Milwaukee, WI 53209, USA Dear Fellow Chemists, To Place Orders Professor Shannon S. Stahl of the Department of Chemistry at the Telephone 800-325-3010 (USA) University of Wisconsin-Madison, kindly suggested that we consider offering KetoABNO, an N-oxyl radical that is a less sterically demanding FAX 800-325-5052 (USA) and more electron-deficient redox mediator than TEMPO and ABNO. It or 414-438-2199 has been employed to catalyze the efficient aerobic oxidation (oxygen Mail P.O. Box 2060 or air) of secondary alcohols to ketones at ambient temperature.1 The Milwaukee, WI 53201, USA reaction is compatible with substrates containing diverse functional groups. KetoABNO also 2 Customer & Technical Services catalyzes a general, mild, and chemoselective aerobic oxidation of amines to imines. Customer Inquiries 800-325-3010 (1) Lauber, M. B.; Stahl, S. S. ACS Catal. 2013, 3, 2612. (2) Sonobe, T.; Oisaki, K.; Kanai, M. Chem. Sci. 2012, 3, 3249. Technical Service 800-325-5832 O SAFC® 800-244-1173 Custom Synthesis 800-244-1173 N Flavors & Fragrances 800-227-4563 O• International 314-771-5765 791814 24-Hour Emergency 314-776-6555 791814 KetoABNO (9-azabicyclo[3.3.1]nonan-3-one-N-oxyl) 250 mg Website sigma-aldrich.com 1 g Email [email protected] We welcome your product ideas. Do you need a product that is not featured on our website or in General Correspondence our catalog? Ask Aldrich! For more than 60 years, your research needs and suggestions have shaped the Aldrich product offering. Email your suggestion to [email protected]. Editor: Sharbil J. Firsan, Ph.D. P.O. Box 2060, Milwaukee, WI 53201, USA [email protected] Subscriptions Scott Batcheller Manager Request your FREE subscription to the Chemistry R&D and Product Management Aldrichimica Acta, through: iPad® App: Aldrich.com/acta-app Web: Aldrich.com/acta TABLE OF CONTENTS Email: [email protected] Ynamides: Powerful and Versatile Reagents for Chemical Synthesis ........................................ 59 Gwilherm Evano,* Cédric Theunissen, and Morgan Lecomte, Université Libre de Bruxelles (ULB) Phone: 800-325-3010 (USA) Cyclic Sulfamidate Enabled Syntheses of Amino Acids, Peptides, Carbohydrates, and Natural Mail: Attn: Marketing Services Products ........................................................................................................................................... 71 Sigma-Aldrich Corporation R. B. Nasir Baig,* Mallikarjuna N. Nadagouda, and Rajender S. Varma,* U.S. Environmental Protection 3050 Spruce Street Agency St. Louis, MO 63103 ABOUT OUR COVER Tamaca Palms (oil on canvas, 67.9 × 91.3 cm) was painted in 1854 by the famed American landscape artist Frederic Edwin Church (1826–1900). Born to a wealthy family, Church took up art studies at an early age and apprenticed for two years with the renowned British landscape painter Thomas Cole, who had relocated to The entire Aldrichimica Acta archive is available at Aldrich.com/acta. the U.S. and co-founded the Hudson River School of landscape painting. Church began his artistic career soon after by painting Aldrichimica Acta (ISSN 0002-5100) is a publication of Aldrich, scenes from the northeastern U.S. in the style of the Hudson a member of the Sigma-Aldrich Group. River School. He won artistic acclaim and achieved commercial success early in his career and, unlike many posthumously Detail from Tamaca Palms. Photo courtesy National ©2015 Sigma-Aldrich Co. LLC. All rights reserved. SIGMA, famous artists, had assembled a small fortune from the sale of Gallery of Art, Washington, DC. SAFC, SIGMA-ALDRICH, ALDRICH, and SUPELCO are trademarks his works by the time he died. of Sigma-Aldrich Co. LLC, registered in the US and other Inspired by the writings of the distinguished naturalist and explorer Alexander von Humboldt, Church countries. Add Aldrich is a trademark of Sigma-Aldrich Co. travelled extensively in South America, Jamaica, the North Atlantic, the Middle East, Italy, and Greece. It LLC. Aldrich brand products are sold through Sigma-Aldrich, was upon his return from a trip to Colombia in 1853 that Church painted Tamaca Palms in his New York studio based on meticulous sketches and observations he had made during the trip.* He often painted Inc. Purchaser must determine the suitability of the products stunning, large, brightly lit, and detailed panoramas that documented the natural features, plants, and for their particular use. Additional terms and conditions may animals of exotic locales. Reminiscent of the romantic tradition in European art, Church’s awe of the beauty apply. Please see product information on the Sigma-Aldrich and majesty of the natural world is unmistakable in his works, where natural features and phenomena are website at www.sigmaaldrich.com and/or on the reverse given prominence over the human element. side of the invoice or packing slip. Sigma-Aldrich Corp. is a This painting is part of the Corcoran Collection at the National Gallery of Art, Washington, DC. subsidiary of Merck KGaA, Darmstadt, Germany. * Could Church have used the sketches that he based Tamaca Palms on as an inspiration for later compositions, iPad is a registered trademark of Apple Inc. especially in his later years? To find out, visit Aldrich.com/acta483 Dynamize your chemistry with ynamides Versatile synthetic handle Electrophiles EWG EWG R N • N R' R R' Ynamide Nucleophiles Despite their huge potential, the inaccessibility and instability of highly reactive nitrogen-substituted alkynes such as ynamines impede numerous synthetic routes. • Total synthesis • Functionalization In collaboration with Professor Gwilherm Evano, • Medicinal chemistry • Asymmetric synthesis Aldrich offers a selection of ynamides—stable surrogates • Heterocyclic chemistry • Organometallic chemistry for ynamines due to the presence of the electron- O withdrawing group (EWG). These strikingly reactive yet O O N stable building blocks are ideal for a multitude of chemo-, O regio-, and stereoselective transformations. Their utility N Ph is extended since the EWG furnishes a versatile chelating 805564 805580 or directing site. Significant scaffolds and reagents in total synthesis and medicinal chemistry, ynamides are O also excellent precursors of highly reactive keteniminium N ions, carbenoids, and many other useful intermediates for the development of new and innovative chemical 805599 O transformations. S N O O O n-C6H13 N 805572 805602 Professor Gwilherm Evano, Cédric Theunissen, and Morgan Lecomte (left to right) References: (1) Evano, G.; Theunissen, C.; Lecomte, M. Aldrichimica Acta 2015, 48, 59. Learn more about Evano ynamides: (2) Evano, G.; Coste, A.; Jouvin, K. Angew. Chem., Int. Ed. 2010, 49, 2840. (3) DeKorver, K. A.; Li, H.; Lohse, A. G.; Hayashi, R.; Lu, Z.; Zhang, Y.; Hsung, R. P. Chem. Rev. 2010, Aldrich.com/ynamides 110, 5064. 84031-b 59 VOL. 48, NO. 3 • 2015 Ynamides: Powerful and Versatile Reagents for Chemical Synthesis Prof. G. Evano Mr. C. Theunissen Mr. M. Lecomte Gwilherm Evano,* Cédric Theunissen, and Morgan Lecomte Laboratoire de Chimie Organique Service de Chimie et PhysicoChimie Organiques Université Libre de Bruxelles (ULB) Avenue F. D. Roosevelt 50, CP160/06 1050 Brussels, Belgium Email: [email protected] Keywords. ynamides; alkynes; organic synthesis; heterocyclic 4. Ynamides as Precursors of Metallated Ketenimines chemistry; reactivity; reactive intermediates. 5. Ynamides as Radical Acceptors 6. Ynamides in Cycloaddition Reactions: Diversity-Oriented Abstract. Ynamides have recently emerged as particularly useful Syntheses of Heterocycles building blocks for chemical synthesis. Their remarkable reactivity has 6.1. [2 + 2] Cycloadditions been exploited in the design of a number of novel synthetic processes 6.2. [3 + 2] Dipolar Cycloadditions and for the generation of otherwise inaccessible reactive intermediates. 6.3. [4 + 2] Cycloadditions The state of the art of the chemistry of ynamides and its impact on 6.4. [2 + 2 + 1] Pauson–Khand Cycloadditions organic synthesis are highlighted in this review, which has been 6.5. [2 + 2 + 2] Cycloadditions structured according to the nature of both the reactive intermediates 7. Cycloisomerization of Ynamides: Rapid Approaches to Diverse generated and the types of reaction they undergo. Nitrogen Heterocycles 8. Polycyclizations of Ynamides: Straightforward Routes to Complex Outline Nitrogen Heterocycles 1 Introduction 9. Ynamides as Building Blocks for the Synthesis of Natural 2. Ynamides as User-Friendly Precursors Products: Enabling New and Original Bond Disconnections 2.1. Of Otherwise Inaccessible Keteniminium Ions 10. Conclusion and Outlook 2.1.1. By Protonation 11. Acknowledgments 2.1.2.
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