About

Jose Roque is an assistant professor of chemistry at Princeton University, specializing in catalysis and synthesis within the field of inorganic chemistry. His research interests lie at the interface of organic and organometallic chemistry, with a focus on developing new reactivity modes to address unsolved problems in catalysis and to expand the reactivity of transition metal complexes. His work aims to solve long-standing challenges in organic synthesis and to provide fundamental insights into chemical reactivity. Born in Havana, Cuba, Roque obtained his B.S. degree in chemistry from Florida International University in 2015, where he worked on the synthetic applications of photochemically produced singlet oxygen. He earned his doctorate at the University of California, Berkeley, in 2020, under Professor Richmond Sarpong, focusing on complex molecule synthesis and skeletal editing strategies. During his doctoral studies, he was a Bristol-Myers Squibb Graduate Fellow and a Reaxys PhD Prize finalist. Following his Ph.D., Roque joined Princeton University as a Presidential Postdoctoral Fellow, working with Professor Paul Chirik on electronically-controlled C–H activation. He launched his independent academic career at Princeton in July 2023.

Research topics

• Chemistry
• Crystallography
• Stereochemistry
• Combinatorial chemistry
• Materials science

Selected publications

• Alkoxide−Bridged Dicobalt(II) Compounds as Precatalysts for C−H Borylation and Application to Late-Stage Functionalization

  ACS Catalysis · 2026-04-22

  articleOpen access

  Treatment of K2[Co2(OtBu)6] with a series of imidazolium salts, RACNC-(HBr)2, provided a route to sterically modified t-butoxide-bridged cobalt compounds, (RACNC)Co2(OtBu)4 (RACNC = N-alkyl-substituted pyridine dicarbene). Characterization by X-ray diffraction and SQUID magnetometry established non-interacting and high-spin dicobalt structures with bridging and terminal alkoxide ligands where the ACNC pincer spans both idealized tetrahedral cobalt atoms. In the presence of excess tert-butyl ethylene (TBE) and B2Pin2, the (RACNC)Co2(OtBu)4, derivatives served as precatalysts for the borylation of electron-rich arenes. Side-by-side comparison enabled the identification of a second-generation pre-catalyst, (EtACNC)Co2(OtBu)4, which displayed improved activity for the borylation of substrates bearing large R groups and aryl-CH3 groups and improved meta selectivity for phenol, aniline, and alkyl benzene derivatives. When applied to biologically active molecules, 11 late-stage functionalizations were achieved, followed by a series of hydroxylations and deuterations, highlighting the application of the developed precatalysts for pharmaceutical research and development. In operando monitoring of the catalytic borylation and the observed site selectivities support formation of monomeric, pincer-supported cobalt(I) complexes as the active catalyst.

  PublisherDOI

• “Store-and-Release” Strategy Enables Nickel-Catalyzed Deaminative Migratory Arylation of Aliphatic Amines

  ChemRxiv · 2026-05-18

  articleSenior author

  While migratory functionalization reactions provide a powerful means to navigate broader chemical space, their application to aliphatic amines remains particularly elusive. Herein, we describe the nickel-catalyzed migratory arylation of aliphatic amines using Katritzky salts enabled by a “store-and-release” strategy. This strategy leverages dihydropyridines, which are traditionally viewed as chemical dead-ends under reductive cross-coupling conditions, as latent reservoirs to store and release translocated alkyl radicals, thereby decoupling the chain-walking event from the cross-coupling cycle. The developed protocol enables migratory functionalization of Katritzky salts derived from a wide range of primary amines, and a variety of aryl and heteroaryl bromides. The reaction exhibits broad functional group tolerance, accommodating alkenes, polar functionalities, and substrates derived from pharmaceutically relevant compounds. This methodology enables expanded small-molecule library synthesis through regiodivergent deaminative arylations. Preliminary mechanistic studies support the “store-and-release” design principle, rendering it as a platform that can be applied for other migratory functionalization reactions.

  PublisherDOI

• Site-Selectivity of C(sp²)–H Oxidative Addition of Fluorinated Arenes with Pyridine(dicarbene) Cobalt(I) Complexes and Aryl Isomerization

  Organometallics · 2025-03-26 · 5 citations

  articleOpen access

  The rate, site-selectivity, and product isomerization of the C(sp2)–H oxidative addition of arenes with pyridine(dicarbene) cobalt methyl and phenyl complexes have been investigated with four representative arenes of varying electronic and steric properties. The rates of C(sp2)–H activation to yield cobalt-aryl products and subsequent aryl isomerization were influenced by the electronic properties of the arene; the relatively electron-poor arene 3-fluorobenzotrifluoride underwent C(sp2)–H activation and isomerization of the cobalt-aryl more than 70 times faster than the more electron-rich substrate, 3-fluoro-N,N,α-trimethylbenzeneacetamide. In all cases, meta-to-fluorine C(sp2)–H oxidative addition was the major product at low conversion, which subsequently isomerized to the ortho isomer over time. Deuterium-labeling experiments and measurement of methane isotopologues establish that the major cobalt-aryl product at early conversion arises from kinetically preferred, meta-selective oxidative addition. Density functional theory calculations support pathways involving cobalt(I)–(III) redox cycles with oxidative addition to cobalt(I) occurring with a relatively high barrier followed by faster reductive elimination. Despite the strong σ-donating properties of the pyridine(dicarbene) pincer ligand, the π-accepting character of the carbene donors lowers the barrier for reductive elimination, and hence, cobalt(III) intermediates have not been observed.

  PublisherOA PDFDOI

• Alkene Borylation–Hydrogenation Enables Highly Active, Site-Selective Cobalt-Catalyzed Borylation

  Journal of the American Chemical Society · 2025-07-18 · 5 citations

  articleOpen access

  A method for promoting highly active and site-selective cobalt-catalyzed C(sp2)–H arene borylation is described. Addition of tert-butyl ethylene (TBE) increased the activity of the cobalt-catalyzed borylation of electron-rich arenes. With monosubstituted anisoles and anilines, synthetically useful site-selectivities favoring the meta-position of the ring were observed. Monitoring the catalytic reaction in situ by 1H NMR spectroscopy established a borylation–hydrogenation sequence of tert-butyl ethylene as being responsible for the increased catalytic activity where borylation of the alkene preceded functionalization of the arene. Added or in situ generated trans-tBuCH═CHBPin served as the active H2 acceptor to overcome the inhibitory effect of HBPin and enabled both HBPin and B2Pin2 to be effective reagents for generating the active cobalt catalyst. Normal primary deuterium isotope effects of 5.0(1.2) and 6.0(2.0) in parallel and 3.1(1) and 3.7(3) in competition for meta and para borylation, respectively, were measured at 23 °C for the catalytic borylation of N-phenylmorpholine, supporting irreversible and rate-determining oxidative addition of the C(sp2)–H bond during the catalytic reaction. The combination of the kinetic isotope effects, in situ reaction monitoring, DFT studies, and stoichiometric experiments support the origin of meta selectivity as arising from irreversible oxidative addition of the meta-C(sp2)–H bond to cobalt(I).

  PublisherOA PDFDOI

• The Role of Boron Reagents in Determining the Site-Selectivity of Pyridine(dicarbene) Cobalt-Catalyzed C–H Borylation of Fluorinated Arenes

  Journal of the American Chemical Society · 2025-04-17 · 7 citations

  articleOpen access

  The origin of the meta- and ortho-to-fluorine site-selectivity in the C(sp2)–H borylation of fluorinated arenes with B2Pin2 and HBPin promoted by pyridine(dicarbene)cobalt catalysts has been investigated. In situ generation of the cobalt(I)-boryl complex and treatment with three representative fluoroarenes established meta-selective C(sp2)–H oxidative addition to form predominantly the meta isomers of the corresponding cobalt(I)-aryl complexes. Attempts to observe or isolate the four-coordinate cobalt(I)-boryl complex yielded the cobalt-hydride dimer, [(iPrACNC)CoH]2, borohydride (iPrACNC)CoH2BPin, or diboryl hydride, (iPrACNC)CoH(BPin)2 depending on the amounts of B2Pin2 and HBPin present. The phosphite derivatives (iPrACNC)CoH(P(OiPr)3) and (iPrACNC)CoBPin(P(OiPr)3) were prepared and crystallographically characterized. In the catalytic borylation of 1,3-difluorobenzene, ortho-to-fluorine cobalt(I)-aryl and borohydride complexes were identified as resting states despite meta-to-fluorine borylation being the major product of catalysis. Deuterium kinetic isotope effects support irreversible but not turnover-limiting C(sp2)–H oxidative addition. Stoichiometric borylation of isolated cobalt(I)-aryl intermediates with B2Pin2 established that the meta-cobalt(I)-aryl was more reactive than the ortho-isomer and accounts for the observed cobalt(I)-aryl resting states. All cobalt(I)-aryl compounds reacted more quickly with HBPin. While ortho-cobalt(I)-aryl compounds yielded arylboronate products with high site-selectivity, meta-cobalt-aryl counterparts yielded a mixture of arylboronate isomers and free arene. Deuterium labeling experiments with DBPin confirmed that HBPin mediates reversible C(sp2)–H oxidative addition. Thus, the overall site-selectivity arises from two reinforcing effects: (i) kinetically meta-selective oxidative addition and (ii) faster reaction of the meta-cobalt-aryl isomer with B2Pin2. As B2Pin2 is converted to HBPin, C(sp2)–H reductive elimination competes against borylation of the meta-cobalt-aryl isomer, resulting in increased ortho-selective borylation.

  PublisherOA PDFDOI

• CCDC 2246989: Experimental Crystal Structure Determination

  The Cambridge Structural Database · 2024-01-06

  datasetOpen access1st authorCorresponding

  An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  PublisherDOI

• CCDC 2246987: Experimental Crystal Structure Determination

  The Cambridge Structural Database · 2024-01-06

  datasetOpen access1st authorCorresponding

  An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  PublisherDOI

• CCDC 2246988: Experimental Crystal Structure Determination

  The Cambridge Structural Database · 2024-01-06

  datasetOpen access1st authorCorresponding

  An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  PublisherDOI

• CCDC 2246986: Experimental Crystal Structure Determination

  The Cambridge Structural Database · 2024-01-06

  datasetOpen access1st authorCorresponding

  An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  PublisherDOI

• Photo- and Metal-Mediated Deconstructive Approaches to Cyclic Aliphatic Amine Diversification

  Journal of the American Chemical Society · 2023-05-12 · 51 citations

  articleOpen access

  Described herein are studies toward the core modification of cyclic aliphatic amines using either a riboflavin/photo-irradiation approach or Cu(I) and Ag(I) to mediate the process. Structural remodeling of cyclic amines is explored through oxidative C–N and C–C bond cleavage using peroxydisulfate (persulfate) as an oxidant. Ring-opening reactions to access linear aldehydes or carboxylic acids with flavin-derived photocatalysis or Cu salts, respectively, are demonstrated. A complementary ring-opening process mediated by Ag(I) facilitates decarboxylative Csp3–Csp2 coupling in Minisci-type reactions through a key alkyl radical intermediate. Heterocycle interconversion is demonstrated through the transformation of N-acyl cyclic amines to oxazines using Cu(II) oxidation of the alkyl radical. These transformations are investigated by computation to inform the proposed mechanistic pathways. Computational studies indicate that persulfate mediates oxidation of cyclic amines with concomitant reduction of riboflavin. Persulfate is subsequently reduced by formal hydride transfer from the reduced riboflavin catalyst. Oxidation of the cyclic aliphatic amines with a Cu(I) salt is proposed to be initiated by homolysis of the peroxy bond of persulfate followed by α-HAT from the cyclic amine and radical recombination to form an α-sulfate adduct, which is hydrolyzed to the hemiaminal. Investigation of the pathway to form oxazines indicates a kinetic preference for cyclization over more typical elimination pathways to form olefins through Cu(II) oxidation of alkyl radicals.

  PublisherOA PDFDOI

Frequent coauthors

• Richmond Sarpong

  University of California, Berkeley

  31 shared

• Djamaladdin G. Musaev

  Atlanta University Center

  22 shared

• Bohyun Park

  Korea Advanced Institute of Science and Technology

  15 shared

• Charles S. Yeung

  Merck & Co., Inc., Rahway, NJ, USA (United States)

  14 shared

• Justin Jurczyk

  University of California, Berkeley

  13 shared

• Jin Su Ham

  University of California, Berkeley

  13 shared

• Liping Xu

  13 shared

• Mu‐Hyun Baik

  12 shared

Labs

• Roque GroupPI

Education

• PhD Candidate, Chemistry

  University of California Berkeley

Awards & honors

• Bristol-Myers Squibb Graduate Fellow in Synthetic Organic Ch…
• Reaxys PhD Prize finalist
• Presidential Postdoctoral Fellow at Princeton University
• Emergent Leader Award (2026)