Stephen Leffler Buchwald

About

Stephen Leffler Buchwald is the Camille Dreyfus Professor of Chemistry at MIT. His research group combines elements of organic synthesis, physical organic chemistry, and organometallic chemistry to develop catalytic processes that address fundamental problems. His work involves inventing and developing new techniques, understanding their mechanisms, and applying them in synthetically interesting contexts. Key areas of his research include the creation and study of new ligands, the design of methods for forming carbon-nitrogen and carbon-fluorine bonds—particularly using metal catalysts based on palladium or copper—and employing mechanistic and structural studies to aid in ligand and catalyst development. Additionally, his group explores continuous flow chemistry using microreactors and capillary tubing to optimize chemical processes on a small scale, leveraging the enhanced heat and mass transfer properties of silicon microreactors.

Research topics

• Combinatorial chemistry
• Organic chemistry
• Chemistry
• Stereochemistry
• Nanotechnology
• Materials science
• Photochemistry
• Inorganic chemistry
• Physical chemistry
• Medicinal chemistry

Selected publications

• CuH-Catalyzed Olefin Functionalization: From Hydroamination to Carbonyl Addition

  Accounts of Chemical Research · 2020 · 449 citations

  Senior authorCorresponding

  In organic synthesis, ligand-modified copper(I) hydride (CuH) complexes have become well-known reagents and catalysts for selective reduction, particularly toward Michael acceptors and carbonyl compounds. Recently, our group and others have found that these hydride complexes undergo migratory insertion (hydrocupration) with relatively unactivated and electronically unpolarized olefins, producing alkylcopper intermediates that can be leveraged to forge a variety of useful bonds. The resulting for…

  DOI

• Microfluidic electrochemistry for single-electron transfer redox-neutral reactions

  Science · 2020 · 319 citations

  )-O cross-coupling. The cathode and anode simultaneously generate the corresponding reactive intermediates, and selective transformation is facilitated by the rapid molecular diffusion across a microfluidic channel that outpaces the decomposition of the intermediates. μRN-eChem was shown to enable a two-step gram-scale electrosynthesis of a nematic liquid crystal compound, demonstrating its practicality.

  DOI

• The Quest for the Ideal Base: Rational Design of a Nickel Precatalyst Enables Mild, Homogeneous C–N Cross-Coupling

  Journal of the American Chemical Society · 2020 · 118 citations

  Senior authorCorresponding

  of the Ni-bound amine and the barrier to reductive elimination from the resultant Ni(II)-amido complex. Moreover, we determined that the preclusion of Lewis acid-base complexation between the Ni catalyst and the base, due to steric factors, is important for avoiding catalyst inhibition.

  DOI

• Evidence for Simultaneous Dearomatization of Two Aromatic Rings under Mild Conditions in Cu(I)-Catalyzed Direct Asymmetric Dearomatization of Pyridine

  Journal of the American Chemical Society · 2020 · 63 citations

  Senior authorCorresponding

  Bis(phosphine) copper hydride complexes are uniquely able to catalyze direct dearomatization of unactivated pyridines with carbon nucleophiles, but the mechanistic basis for this result has been unclear. Here we show that, contrary to our initial hypotheses, the catalytic mechanism is monometallic and proceeds via dearomative rearrangement of the phenethylcopper nucleophile to a Cpara-metalated form prior to reaction at heterocycle C4. Our studies support an unexpected heterocycle-promoted pathw…

  DOI

• Cu-Catalyzed Amination of Base-Sensitive Aryl Bromides and the Chemoselective N- and O-Arylation of Amino Alcohols

  Journal of the American Chemical Society · 2024-06-26 · 47 citations

  articleOpen accessSenior authorCorresponding

  We report a general and functional-group-tolerant method for the Cu-catalyzed amination of base-sensitive aryl bromides including substrates possessing acidic functional groups and small five-membered heteroarenes. The results presented herein substantially expand the scope of Cu-catalyzed C–N coupling reactions. The combination of L8, an anionic N1,N2-diarylbenzene-1,2-diamine ligand, along with the mild base NaOTMS leads to the formation of a stable yet reactive catalyst that resists deactivat…

  PublisherOA PDFDOI

Recent grants

• NIH Grant R37GM046059

  NIH · $8.1M · 2010

• NIH Grant S10RR013886

  NIH · $296k · 2000

• Metal-Catalyzed Methods for Organic Synthesis

  NIH · $10.2M · 2017–2027

Frequent coauthors

• Bradley L. Pentelute

  Massachusetts Institute of Technology

  54 shared

• Brett P. Fors

  University of California, Santa Barbara

  49 shared

• Timothy E. Barder

  38 shared

• Phillip J. Milner

  University of California, Berkeley

  38 shared

• Mingjuan Su

  Massachusetts Institute of Technology

  38 shared

• John P. Wolfe

  University of Michigan–Ann Arbor

  38 shared

• Richard Y. Liu

  Duke University

  38 shared

• Klavs F. Jensen

  Massachusetts Institute of Technology

  34 shared

Similar researchers at Massachusetts Institute of Technology

• Moungi Bawendih-181
• Robert Guy Griffinh-121
• Arup K Chakrabortyh-89