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Acta Volume 45, 2012 VOL. 45, NO. 1 • 2012 “Designer”-Surfactant-Enabled Cross-Couplings in M ICHI ICA A DR C L TA A Water at Room Temperature 2 8 th 0 6 1 9 2 The Growing Impact of Niobium in Organic 1 4 A N 5 Y R Synthesis and Catalysis N I V E R S A For convenient General Reaction Equation trifluoromethylation N N Cu I CF3 of aryl iodides. CF 3 DMF, 25-50 oC, 18 h Representative Reaction Scope CF3 CF3 CF3 H Me Hartwig Trifluoromethylations MeO 96% O 89% O 93% Aldrich Chemistry would like to introduce Trifluoromethylator™, a highly efficient trifluoromethylation reagent from the CF3 CF3 CF3 laboratory of Professor John Hartwig and Catylix, Inc. Trifluoromethylator™ (Phen)Cu-CF3 (Prod. No. L510009) is a EtO2C BnO AcHN convenient, thermally stable, single-component reagent for 94% 89% 85% the trifluoromethylation of aryl iodides. It provides: O CF CF CF • Tolerance of electrophilic functional groups, including 3 3 H 3 aldehydes, nitroarenes, ketones and esters O2N Ph OAc • High yields under mild conditions for electron-rich and quant. 83% 68% OMe electron-deficient iodoarenes, as well as sterically hindered iodoarenes O BOM Br CF3 CF3 Increased flexibility for carrying out ester hydrolysis in N • O your synthesis O N 89% 78% BOM CF3 Cl N N F3C CF3 Cu N CF3 Cl N CO2Et L510009 89% 99% Boc 69% Solutions of Trifluoromethylator™ in toluene CF3 CF3 are safe to use at process scale. n-C6H11 99% OMOM OMOM To request custom and bulk quantities Reference: Morimoto, H.; Tsubogo, T.; Litvinas, N. D.; Hartwig, J. F. CF3 of Trifluoromethylator™, visit Angew. Chem. Int. Ed. 2011, 50, 3793. 97% Aldrich.com/catylix Trifl uoromethylator is a trademark of Catylix, Inc. 78095 78095_ALD Trifluoromethylator Ad (Acta 45.1).indd 1 3/28/2012 11:41:17 AM 1 VOL. 45, NO. 1 • 2012 Aldrich Chemical Co., Inc. “PLEASE BOTHER US.” 6000 N. Teutonia Ave. Milwaukee, WI 53209, USA Dear Fellow Chemists, To Place Orders We have had many suggestions for the DalPhos ligands shown below. These were recently developed by Professor Mark Stradiotto and his group Telephone 800-325-3010 (USA) at Dalhousie University. Both are air-stable, chelating N,P ligands that enable FAX 800-325-5052 (USA) the Pd-catalyzed cross-coupling of ammonia. Mor-DalPhos is also effective in or 414-438-2199 coupling hydrazine and acetone, and in the gold–catalyzed hydroamination. Mail P.O. Box 2060 The catalysts are used with low loadings and exhibit excellent functional Milwaukee, WI 53201, USA group tolerance and chemoselectivty. Customer & Technical Services (a) Lundgren, R. J.; Peters, B. D.; Alsabeh, P. G.; Stradiotto, M. Angew. Chem., Int. Ed. 2010, 49, 4071. (b) Lundgren, R. J.; Stradiotto, M. Angew. Chem., Int. Ed. 2010, 49, 8686. Customer Inquiries 800-325-3010 Technical Service 800-231-8327 N CH SAFC® 800-244-1173 N 3 P O Custom Synthesis 800-244-1173 P CH3 Flavors & Fragrances 800-227-4563 International 414-438-3850 24-Hour Emergency 414-438-3850 751618 751413 Website sigma-aldrich.com 751618 Di(1-adamantyl)-2-morpholinophenylphosphine (Mor-DalPhos) 250 mg Email [email protected] 1 g 751413 Di(1-adamantyl)-2-dimethylaminophenylphosphine (Me-DalPhos) 250 mg General Correspondence 1 g Editor: Sharbil J. Firsan, Ph.D. P.O. Box 2988, Milwaukee, WI 53201, USA We welcome fresh product ideas from you. Do you need a compound that isn’t listed in our [email protected] catalog? Ask Aldrich! For over 60 years, your research needs and suggestions have shaped the Aldrich product offering. To submit your suggestion visit Aldrich.com/pleasebotherus. Subscriptions Request your FREE subscription to the Aldrichimica Acta, through: John Radke Web: Aldrich.com/acta Director of Marketing, Chemistry Email: [email protected] TABLE OF CONTENTS “Designer”-Surfactant-Enabled Cross-Couplings in Water at Room Temperature ................3 Phone: 800-325-3010 (USA) Bruce H. Lipshutz* and Subir Ghorai, University of California, Santa Barbara, and Sigma-Aldrich Co., Mail: Attn: Mailroom Sheboygan Falls, Wisconsin Aldrich Chemical Co., Inc. The Growing Impact of Niobium in Organic Synthesis and Catalysis .................................... 19 Sigma-Aldrich Corporation Valdemar Lacerda, Jr.,* Deborah Araujo dos Santos, Luiz Carlos da Silva-Filho, Sandro José Greco, and P.O. Box 2988 Reginaldo Bezerra dos Santos, Universidade Federal do Espírito Santo and Universidade Estadual Milwaukee, WI 53201-2988 Paulista (Brasil) ABOUT OUR COVER Venice: The Dogana and San Giorgio Maggiore (oil on canvas, 91.5 × 122.0 cm) was completed in 1834 by Joseph Mallord William Turner (London, 1775–1851). A prolific British artist and an influential member of the Romantic Movement of the late eighteenth and first half of the nineteenth century, he elevated landscape painting to a level not achieved before The entire Aldrichimica Acta archive is also available free of and introduced several innovations to the genre. His talent charge at Aldrich.com/acta. manifested itself very early in life, and he was much admired Aldrichimica Acta (ISSN 0002-5100) is a publication of Aldrich. as an artist in life and death, with institutions, works, and artistic Detail from Venice: The Dogana and San Giorgio Maggiore. Aldrich is a member of the Sigma-Aldrich Group. prizes dedicated to preserving his legacy. Photograph © Board of Trustees, National Gallery of Art, Washington. This painting depicts a bustling maritime scene in the Grand Canal of Venice, which Turner had visited several ©2012 Sigma-Aldrich Co. LLC. All rights reserved. SIGMA, times. (Another Venetian cityscape, painted seven years earlier by another British Romantic Movement artist, R. SAFC, SIGMA-ALDRICH, ALDRICH, and SUPELCO are trademarks P. Bonington, has graced the cover of Aldrichimica Acta, Vol. 43, No. 1.) Turner intended this work as a celebration of Sigma-Aldrich Co. LLC, registered in the US and other of commerce, as symbolized by the statue of Fortune atop the Dogana (Customs building) in the foreground. countries. Add Aldrich is a trademark of Sigma-Aldrich Co. LLC. Aldrich brand products are sold through Sigma-Aldrich, Inc. While Turner was not concerned with a faithful depiction of the scene, as evidenced by the apparent widening Purchaser must determine the suitability of the product(s) of the canal and placement of San Giorgio’s church, his skill as a draftsman and his mastery of perspective for their particular use. Additional terms and conditions may drawing are evident in his precise, linear rendering of the buildings and sharp angles. His color combinations, apply. Please see product information on the Sigma-Aldrich freely handled layers of paint, and the sparkling water and light sky exemplify his lifelong preoccupation with website at www.sigmaaldrich.com and/or on the reverse side the effects and significance of light in an awe-inspiring natural world. of the invoice or packing slip. This painting is part of the Widener Collection at the National Gallery of Art, Washington, DC. TPGS-750-M Cat. No. 733857 O CH3 O O H3CO O H3C n O O CH3 Want to n = ~16 H3C H C CH3 3 run transition- 3 transition metal catalyst partner A TPGS-750-M metal-catalyzed + product C water, rt reactions in water at partner B Heck Sonogashira room temperature? O O MeO 97% 99% Suzuki-Miyaura Negishi-like CO Et OMe 2 4 87% (E/Z = 99/1) Congratulations to Professor Bruce Lipshutz, University of 88% California, Santa Barbara, winner of the 2011 Presidential Green Chemistry Challenge Award: Academic, for the development C-H activation Fujiwara-Moritani of TPGS-750-M, an amphiphile that enables transition-metal- OMe CO n-Bu catalyzed reactions to be run in water, at room temperature. 2 H H N Applicable to many transition-metal-catalyzed reactions N N • O O • Scalable OMe OMe • Highly water-soluble 68% 83% • No frothing at workup ring-closing metathesis cross-metathesis Easily separated from reaction product(s) and recycled • N O Ts OTBS • Amenable to high-throughput screening 88% 74% aminations H N For greener chemistry N in your lab, Add Aldrich. 98% Aldrich.com/tpgs750m Lipshutz, B. H. et al. J. Org. Chem. 2011, 76, 4379. 78375 78375_ALD Lipshutz TPGS-750-M Ad (Acta 45.1).indd 1 3/23/2012 11:16:59 AM 3 VOL. 45, NO. 1 • 2012 “Designer”-Surfactant-Enabled Cross-Couplings in Water at Room Temperature Bruce H. Lipshutz*,a and Subir Ghoraib a Department of Chemistry & Biochemistry University of California Santa Barbara, CA 93106, USA Email: [email protected] b Catalysis R&D Sigma-Aldrich Co. 5485 County Road V Prof. Bruce H. Lipshutz Dr. Subir Ghorai Sheboygan Falls, WI 53085, USA Keywords. green chemistry; micellar catalysis; designer surfactants; within their lipophilic cores (Figure 1). While a disaster of this cross-couplings; PTS; TPGS-750-M. magnitude needs the tincture of time to assess its full impact on the environment, from a purely chemical perspective, tremendous hope Abstract. New methodologies are discussed that allow for several has been placed on these surfactants in anticipation that they will commonly used transition-metal-catalyzed coupling reactions to prevent further damage to wildlife and shores. be conducted within aqueous micellar nanoparticles at ambient This micellar chemistry undertaken on a grand scale by the temperatures. petroleum industry highlights the potential for simple amphiphilic molecules to “solubilize” organic materials in a purely aqueous Outline medium. Many other industries use surfactants routinely; examples 1. Introduction include paint, cosmetics, cleaning, leather, carpet, asphalt, and pulp 2. Background & paper companies.3 Relatively small amounts have been used for 3. Chemistry in PTS–H2O, an Update: a 1st-Generation Amphiphile decades in highly controlled environments, e.g., as “excipients” in for Transition-Metal-Catalyzed Cross-Couplings the pharmaceutical arena, to help increase dissolution of otherwise 3.1.
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