David MacMillan

Learn More
Photoredox catalysis and organocatalysis represent two powerful fields of molecule activation that have found widespread application in the areas of inorganic and organic chemistry, respectively. We merged these two catalysis fields to solve problems in asymmetric chemical synthesis. Specifically, the enantioselective intermolecular alpha-alkylation of(More)
The direct β-activation of saturated aldehydes and ketones has long been an elusive transformation. We found that photoredox catalysis in combination with organocatalysis can lead to the transient generation of 5π-electron β-enaminyl radicals from ketones and aldehydes that rapidly couple with cyano-substituted aryl rings at the carbonyl β-position. This(More)
The identification of new chemical strategies that allow increasingly rapid access to structural complexity remains a preeminent goal for the chemical sciences. While the total synthesis approach to molecular complexity has traditionally focused upon a " stop and go " sequence of individual reactions, it is intriguing to consider that biological systems(More)
Organofluorine compounds possess unique physical properties that are exploited in a wide range of applications such as dyes, polymers, agrochemicals, and pharmaceuticals. 1 In medicinal chemistry, for example, valuable physiological properties are often conferred on " drug-like " molecules via the incorporation of CF 3 groups that enhance binding(More)
Direct C-H functionalization and arylation of benzyl ethers has been accomplished via photoredox organocatalysis. The productive merger of a thiol catalyst and a commercially available iridium photoredox catalyst in the presence of household light directly affords benzylic arylation products in good to excellent yield. The utility of this methodology is(More)
The discovery of new strategies that emulate natures capacity to rapidly construct architectural complexity continues to be a central focus for research and development in the chemical sciences. [1] Recently, our laboratory disclosed the concept of organocascade catalysis, [2–4] a new chemical paradigm that combines two modes of catalyst activation (iminium(More)
Serendipity has long been a welcome yet elusive phenomenon in the advancement of chemistry. We sought to exploit serendipity as a means of rapidly identifying unanticipated chemical transformations. By using a high-throughput, automated workflow and evaluating a large number of random reactions, we have discovered a photoredox-catalyzed C-H arylation(More)
The direct functionalization of unactivated sp(3) C-H bonds is still one of the most challenging problems facing synthetic organic chemists. The appeal of such transformations derives from their capacity to facilitate the construction of complex organic molecules via the coupling of simple and otherwise inert building blocks, without introducing extraneous(More)
The first Suzuki cross-coupling reaction of aryltrimethylammonium triflates based on the use of an IMes.Ni(0) catalyst system is described. A wide range of electron-withdrawing and electron-donating substituents are tolerated on both the aryltrimethylammonium triflate and the boronic acid components of this reaction. In addition to arylboronic acids, the(More)