Through the use of Pd2(dba)3/P(t-Bu)3 as a catalyst, wide range aryl and vinyl halides, including chlorides, undergo Suzuki cross-coupling with arylboronic acids in very good yield, typically at room temperature; through Pd(OAc)2/PCy3, diverse array triflates react cleanly temperature. Together, these two catalyst systems cover broad spectrum commonly encountered substrates for couplings. Furthermore, they display novel reactivity patterns, such selective by an chloride preference to...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTRing-Closing Metathesis and Related Processes in Organic SynthesisRobert H. Grubbs, Scott J. Miller, Gregory C. FuCite this: Acc. Chem. Res. 1995, 28, 11, 446–452Publication Date (Print):November 1, 1995Publication History Published online1 May 2002Published inissue 1 November 1995https://pubs.acs.org/doi/10.1021/ar00059a002https://doi.org/10.1021/ar00059a002research-articleACS PublicationsRequest reuse permissionsArticle...

Metal-catalyzed coupling reactions of aryl electrophiles with organometallics and olefins serve as unusually effective tools for forming new carbon−carbon bonds. By 1998, researchers had developed catalysts that achieved iodides, bromides, triflates. Nevertheless, many noteworthy challenges remained; among them were couplings triflates under mild conditions (at room temperature, example), hindered reaction partners, inexpensive chlorides. This Account highlights some the progress has been...

Copper's light touch forges C-N bonds Organic photochemistry has traditionally relied on excitation in the ultraviolet, where carbon-based compounds tend to absorb. Over past decade, field undergone a renaissance as that absorb visible have proven be versatile catalysts for organic reactions. For most part, however, these contained rare metals such ruthenium or iridium. Kainz et al. now report blue light-driven bond-forming reaction catalyzed by Earth-abundant copper (see Perspective...

From only commercially available reagents a wide array of Suzuki cross-couplings aryl chlorides with arylboronic acids can be effected in excellent yield [Eq. (a)]. This development provides general solution to long-standing limitation this extremely powerful process-the poor reactivity inexpensive and readily accessible chlorides. dba=dibenzylideneacetone.

In the presence of Cy2NMe, Pd/P(t-Bu)3 serves as an exceptionally mild and versatile catalyst for Heck reactions aryl chlorides bromides. A sterically electronically diverse array bromides, well activated chlorides, couple with a range mono- disubstituted olefins at room temperature, furnishing arylated product high E/Z stereoselection. The corresponding broad spectrum electron-neutral electron-rich proceed elevated also selectivity. terms scope mildness, Pd/P(t-Bu)3/Cy2NMe represents...

Trialkylphosphines furnish unusual, sometimes unique, reactivity in a range of transformations. Unfortunately, their utility is compromised by sensitivity to oxidation. We have examined simple but powerful strategy for addressing this problem: convert air-sensitive trialkylphosphines into air-stable phosphonium salts via protonation on phosphorus. These robust serve as direct replacements the corresponding phosphines (simple deprotonation under reaction conditions Brønsted base liberates...

Palladiumkatalysierte Kupplungen gehören zu den leistungsfähigsten und vielseitigsten Reaktionen, die dem organischen Chemiker für Synthese zur Verfügung stehen. Ihre große Beliebtheit rührt teilweise daher, dass sie bei Umsetzungen gewöhnlich viele funktionelle Gruppen tolerieren, was ihre breite Verwendung in vielen Bereichen ermöglicht. Allerdings unterlagen palladiumkatalysierten jahrelang großen Einschränkungen durch geringe Reaktivität der Arylchloride; diese Verbindungen sind Bezug...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCatalytic ring-closing metathesis of functionalized dienes by a ruthenium carbene complexGregory C. Fu, SonBinh T. Nguyen, and Robert H. GrubbsCite this: J. Am. Chem. Soc. 1993, 115, 21, 9856–9857Publication Date (Print):October 1, 1993Publication History Published online1 May 2002Published inissue 1 October 1993https://pubs.acs.org/doi/10.1021/ja00074a085https://doi.org/10.1021/ja00074a085research-articleACS PublicationsRequest reuse...

Abstract Until recently, there had been a widespread perception that unactivated, β‐hydrogen‐containing alkyl halides/pseudohalides are not suitable partners for nickel‐catalyzed coupling reactions. During the past several years, number of reports have dispelled this misconception by demonstrating diverse array electrophiles and organometallic reagents can in fact be efficiently cross‐coupled.

Ullman Upgrade Precious metals may dominate contemporary catalysis, but the early development of synthetic organic chemistry relied on more abundant elements—a strategy that chemists are returning to now for sake sustainability. Copper-mediated coupling aryl halides with amines was reported by than a century ago and remains in use today synthesis certain compounds. However, reaction generally requires high temperature proceed efficiently. Creutz et al. (p. 647 ) have developed photochemical...

An asymmetric decarboxylative Csp(3)-Csp(2) cross-coupling has been achieved via the synergistic merger of photoredox and nickel catalysis. This mild, operationally simple protocol transforms a wide variety naturally abundant α-amino acids readily available aryl halides into valuable chiral benzylic amines in high enantiomeric excess, thereby producing motifs found pharmacologically active agents.

Whereas chiral Lewis acid catalysis has been intensively investigated, base (nucleophilic) comparatively neglected. We have developed "planar-chiral" derivatives of 4-(dimethylamino)pyridine (DMAP), a highly versatile nucleophilic catalyst, that are effective in diverse array processes, including the Staudinger synthesis beta-lactams, acylation silyl ketene acetals, and kinetic resolution amines.

Pd/P(t-Bu)3 serves as an unusually reactive catalyst for Stille reactions of aryl chlorides and bromides, providing solutions to a number long-standing challenges. An unprecedented array can be cross-coupled with range organotin reagents, including SnBu4. Very hindered biaryls (e.g., tetra-ortho-substituted) synthesized, coupled in the presence triflates. The method is user-friendly, since commercially available complex, Pd(P(t-Bu)3)2, effective. also functions active furnishing first...

ADVERTISEMENT RETURN TO ISSUEPREVLetterNEXTPd(PhCN)2Cl2/P(t-Bu)3: A Versatile Catalyst for Sonogashira Reactions of Aryl Bromides at Room TemperatureThomas Hundertmark, Adam F. Littke, Stephen L. Buchwald, and Gregory C. FuView Author Information Department Chemistry, Massachusetts Institute Technology, Cambridge, 02139 Cite this: Org. Lett. 2000, 2, 12, 1729–1731Publication Date (Web):May 18, 2000Publication History Received5 April 2000Published online18 May inissue 1 June...

A Pd/N-heterocyclic carbene-based catalyst achieves the Sonogashira coupling of an array functionalized, β-hydrogen-containing alkyl bromides and iodides under mild conditions. By furnishing first example a nonphosphine-based palladium for cross-coupling unactivated electrophiles, this study provides impetus future efforts at development that extend beyond phosphine ligands.

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTRoom-Temperature Alkyl−Alkyl Suzuki Cross-Coupling of Alkyl Bromides that Possess β HydrogensMatthew R. Netherton, Chaoyang Dai, Klaus Neuschütz, and Gregory C. FuView Author Information Department Chemistry Massachusetts Institute Technology Cambridge, 02139 Cite this: J. Am. Chem. Soc. 2001, 123, 41, 10099–10100Publication Date (Web):September 21, 2001Publication History Received30 May 2001Published online21 September inissue 1 October...

Although nickel-catalyzed stereoconvergent couplings of racemic alkyl electrophiles are emerging as a powerful tool in organic chemistry, to date there have been no systematic mechanistic studies such processes. Herein, we examine the pathway for enantioselective Negishi arylations secondary propargylic bromides, and provide evidence an unanticipated radical chain wherein oxidative addition C-Br bond occurs through bimetallic mechanism. In particular, crystallographically characterized...

With a single protocol, commercially available Pd(P(t-Bu)(3))(2) can effect the Negishi cross-coupling of wide range aryl and vinyl chlorides with aryl- alkylzinc reagents. The process tolerates nitro groups, it efficiently generates sterically hindered biaryls. In addition, high turnover number (>3000) be achieved.

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTHeck Reactions in the Presence of P(t-Bu)3: Expanded Scope and Milder Reaction Conditions for Coupling Aryl ChloridesAdam F. Littke Gregory C. FuView Author Information Department Chemistry, Massachusetts Institute Technology, Cambridge, 02139 Cite this: J. Org. Chem. 1999, 64, 1, 10–11Publication Date (Web):December 19, 1998Publication History Received5 October 1998Published online19 December inissue 1 January...