Article
Chemistry, Multidisciplinary
Yulin Han, Anni Qin, Qian Zhang, Xue Zhang, Hui Qian, Shengming Ma
Summary: The Rh-catalyzed reaction allows for the efficient synthesis of cis-fused bicyclic products with excellent selectivity and tolerance towards synthetically useful functional groups. The proposed mechanism involves the rapid racemization of the allene moiety in the starting materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Anding Li, Ziru He, Bingyan Liu, Zhen Yang, Zichun Zhang
Summary: In this study, a concise and stereoselective total synthesis of (+/-)-cephanolide B was accomplished in 15 steps. The key steps in the synthesis included an intermolecular Diels-Alder reaction, a tandem reaction featuring intramolecular Pauson-Khand reaction, 6 pi-electrocyclization, and oxidative aromatization to construct the ABC-tricyclic rings (6-5-6), as well as a phthaloyl peroxide-mediated arene oxygenation to install the C-13 phenol group.
Article
Chemistry, Physical
Lauren C. Burrows, Luke T. Jesikiewicz, Peng Liu, Kay M. Brummond
Summary: The study investigated the effects of different ligands on the reactivity and selectivity of enyne PKRs using Rh(I) metal complexes. Experimental results showed that the type of ligand significantly influenced the reaction rate and enantioselectivity. DFT calculations revealed the reaction mechanism and key steps involved in the process.
Article
Chemistry, Physical
Takeshi Yasui, Keiji Yamada, Rine Tatsumi, Yoshihiko Yamamoto
Summary: In this study, a method for generating vinylallenes through cobalt/photoredox dual-catalysis was reported, allowing the formal 1,8-acyloxy migration of 1,6-diynyl esters. A cascade reaction involving 1,8-acyloxy migration/6 pi-electrocyclization was demonstrated using (hetero)aryl-substituted 1,6-diynyl esters, leading to the formation of arenol derivatives, and the method was also applied to cascade cyclizations involving [2 + 2] or [4 + 2] cycloadditions to furnish various polycyclic molecules.
Article
Chemistry, Organic
Alison R. Cochrane, William J. Kerr, Laura C. Paterson, Colin M. Pearson, Paul Shaw
Summary: The development of a sulfide-promoted, microwave-assisted Pauson-Khand reaction enables the formation of fused cyclopentenones using sub-stoichiometric quantities of a cobalt mediator in rapid reaction times and without the need for an external source of toxic carbon monoxide gas. This protocol is applicable to both intra- and intermolecular Pauson-Khand reaction examples.
Article
Chemistry, Multidisciplinary
Deevi Basavaiah, Gangadhararao Golime, Shivalal Banoth, Saidulu Todeti
Summary: This study presents the first example of an umpolung strategy for intermolecular [2 + 2 + 1] cycloaddition between two aryl aldehydes and a nitrile, resulting in the formation of N-C, O-C, and C-C bonds and providing a straightforward synthetic protocol for obtaining 2,4,5-trisubstituted oxazoles.
Article
Chemistry, Multidisciplinary
Hui Wang, Yi Liu, Hongyuan Zhang, Baochao Yang, Haibing He, Shuanhu Gao
Summary: The asymmetric total syntheses of cephalotaxus C19 diterpenoids, which possess a unique cycloheptene A ring with a chiralmethyl group at C-12, were achieved using a universal strategy. Six members, including previously unreported compounds, were successfully synthesized. The concise approach involved a Nicholas/Hosomi-Sakurai cascade reaction to generate the cycloheptene ring with a chiral methyl group, followed by an intramolecular Pauson-Khand reaction for the construction of the target molecules' complete skeleton. This work provides a new strategy for the synthetic analysis of cephalotaxus diterpenoids and structurally related natural products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Zhen Yang
Summary: The total synthesis endeavors contribute to the discovery and invention of new synthetic reactions to advance organic synthesis. Bioactive compounds share common features, such as molecular complexity, protein-binding ability, structural rigidity, and three-dimensionality. Total synthesis offers an alternative solution for generating scarce natural products and their derivatives for studying their biological functions.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Applied
Joan Salto, Maria Biosca, Oscar Pamies, Montserrat Dieguez
Summary: A set of complex tricyclic compounds containing multiple functional groups and stereogenic centers has been synthesized in only two steps with excellent diastereo- and enantioselectivities, using a highly versatile and enantioselective Pd-catalyzed reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Ding Ma, Naifeng Hu, Junli Ao, Shaoli Zang, Guo Yu, Guangxin Liang
Summary: Pauson-Khand reactions with concomitant C-O bond cleavage have been developed for constructing complex bicyclic ring systems with precise control over regio- and stereochemistry. The mechanism behind this reaction has been proposed based on deuterium labelling experiments.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Multidisciplinary
Ashish Yamini, Ashish Kumar, Pralay Das
Summary: This article summarizes the main developments achieved on rhodium catalyst in the area of carbonylative heterocyclic synthesis over the past 20 years.
Article
Chemistry, Multidisciplinary
Ridge Michael P. Ylagan, Eric Jaewon Lee, Daniela E. Negru, Paolo Ricci, Bohyun Park, Haram Ryu, Mu-Hyun Baik, P. Andrew Evans
Summary: We report an enantioselective rhodium(I)-catalyzed Pauson-Khand reaction using 1,6-chloroenynes that contain challenging 1,1-disubstituted olefins. Unlike previous studies, this new approach allows for a wider range of substrates, including both carbon and heteroatom tethers with polar and non-polar substituents on the alkene. DFT calculations reveal the critical role of the halide, which pre-polarizes the alkyne and provides the appropriate steric profile for a favorable interaction with the chiral diphosphine ligand.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Lisa-Catherine Rosenbaum, Maximilian Haefner, Tanja Gaich
Summary: A racemic and scalable enantioselective total synthesis of (+)-waihoensene was achieved, featuring an angular triquinane substructure with an all-cis-fused tetracyclic backbone and six contiguous stereocenters, four of which are quaternary. Enantioselectivity was introduced at an early stage, and key structural features were efficiently installed through several diastereoselective reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Paul Shaw, Storm J. Hassell-Hart, Gayle E. Douglas, Andrew G. Malcolm, Alan R. Kennedy, Gemma White, Laura C. Paterson, William J. Kerr
Summary: In this study, we applied silyl enol ether moieties as efficient alkene coupling partners within cobalt-mediated intramolecular Pauson-Khand reactions. This cyclization strategy delivers valuable oxygenated cyclopentenone products in high yields and allows for the incorporation of a variety of decorated structures.
Article
Chemistry, Physical
John M. Halford-McGuff, Alexandra M. Z. Slawin, Allan J. B. Watson
Summary: This article presents a predictive model for the reactivity and turnover of the Rh-catalyzed [2 + 2 + 2] cycloaddition of diynes and alkynes. Contrary to the proposed electronic model, this model suggests that the reaction is predominantly driven by steric effects, and turnover is proportional to alkyne steric parameters. The model allows for the prediction of catalyst loading, turnover, and reaction yield based on the assessment of the alkyne's steric parameter.
Article
Chemistry, Organic
Mohammed H. Al-Huniti, Jose Rivera-Chavez, Katsuya L. Colon, Jarrod L. Stanley, Joanna E. Burdette, Cedric J. Pearce, Nicholas H. Oberlies, Mitchell P. Croatt
Article
Biochemistry & Molecular Biology
Ghina'a I. Abu Deiab, Mitchell P. Croatt
BIOORGANIC & MEDICINAL CHEMISTRY
(2019)
Article
Chemistry, Organic
Mohammed H. Al-Huniti, Mark A. Perez, Matthew K. Garr, Mitchell P. Croatt
Article
Chemistry, Inorganic & Nuclear
Kate E. McPherson, Mitchell P. Croatt, Andrew T. Morehead, Andrew L. Sargent
Review
Chemistry, Organic
Mohammed H. Al-Huniti, Mitchell P. Croatt
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Biotechnology & Applied Microbiology
Zeinab Y. Al Subeh, Huzefa A. Raja, Jennifer C. Obike, Cedric J. Pearce, Mitchell P. Croatt, Nicholas H. Oberlies
Summary: This study aimed to identify fungi that biosynthesize compounds 1 and 2, optimize fermentation conditions on a lab scale, and develop straightforward purification processes. Gram-scale quantities of RALs and other compounds were successfully obtained as a result.
JOURNAL OF ANTIBIOTICS
(2021)
Review
Chemistry, Medicinal
Ghina'a I. Abu Deiab, Mitchell P. Croatt
Summary: This review focuses on the discovery and chemistry of prostacyclin, as well as the design and synthesis of analogues with improved stability. It also provides a comparison of structural modifications and clinical effects of current and emerging drugs.
MEDICINAL CHEMISTRY RESEARCH
(2022)
Article
Chemistry, Organic
Khyarul Alam, Elvis C. McFee, Mitchell P. Croatt
Summary: The dehydration of maleamic acids using methanesulfonyl chloride as a dehydrating agent to selectively and rapidly generate isomaleimides is reported. The protocol demonstrated good to excellent yields for a variety of maleamic acid derivatives. Adapting this procedure for flow synthesis resulted in increased efficiency and decreased reaction times. Furthermore, maleic anhydride can be converted into the desired isomaleimide in a two-step, one-flask operation.
SYNTHESIS-STUTTGART
(2022)
Article
Plant Sciences
Zeinab Y. Al Subeh, Tian Li, Abraham Ustoyev, Jennifer C. Obike, Philip M. West, Manead Khin, Joanna E. Burdette, Cedric J. Pearce, Nicholas H. Oberlies, Mitchell P. Croatt
Summary: In this study, a step-economical approach was used to synthesize 35 C8-C9 diol analogues through nonselective reactions, showing their potential as anti-tumor agents with TAK1 inhibitory activity and cytotoxicity against ovarian and breast cancer cell lines.
JOURNAL OF NATURAL PRODUCTS
(2022)
Article
Chemistry, Medicinal
Laura Figuerola-Asencio, Paula Morales, Pingwei Zhao, Dow P. Hurst, Sommayah S. Sayed, Katsuya L. Colon, Maria Gomez-Canas, Javier Fernandez-Ruiz, Mitchell P. Croatt, Patricia H. Reggio, Mary E. Abood, Nadine Jagerovic
Summary: This study focused on the exploration of GPR55 receptor and identified a thienopyrimidine scaffold-based GPR55 antagonist. The GPR55 activity of newly synthesized compounds was evaluated, and some derivatives with functional efficacy and selectivity against CB1 and CB2 cannabinoid receptors were discovered.
ACS MEDICINAL CHEMISTRY LETTERS
(2023)
News Item
Chemistry, Multidisciplinary
Abraham Ustoyev, Mitchell P. Croatt
Summary: Dipolar cycloadditions are effective for forming heterocyclic systems from simple starting materials. However, the utilization of arenes as dipolarophiles remains underexplored. In this study, the intramolecular dipolar cycloaddition of aromatic rings was successfully achieved using in situ generated diazoalkenes, resulting in the formation of bicyclic or tricyclic heterocycles.
Article
Biochemistry & Molecular Biology
Noemi D. Paguigan, Mohammed H. Al-Huniti, Huzefa A. Raja, Austin Czarnecki, Joanna E. Burdette, Mariana Gonzalez-Medina, Jose L. Medina-Franco, Stephen J. Polyak, Cedric J. Pearce, Mitchell P. Croatt, Nicholas H. Oberlies
BIOORGANIC & MEDICINAL CHEMISTRY
(2017)
Article
Biochemistry & Molecular Biology
Lara Fakhouri, Christopher D. Cook, Mohammed H. Al-Huniti, Linda M. Console-Bram, Dow P. Hurst, Michael B. S. Spano, Daniel J. Nasrallah, Marc G. Caron, Larry S. Barak, Patricia H. Reggio, Mary E. Abood, Mitchell P. Croatt
BIOORGANIC & MEDICINAL CHEMISTRY
(2017)
Article
Chemistry, Medicinal
Manahil M. Abdalhameed, Pingwei Zhao, Dow P. Hurst, Patricia H. Reggio, Mary E. Abood, Mitchell P. Croatt
BIOORGANIC & MEDICINAL CHEMISTRY LETTERS
(2017)
Article
Chemistry, Organic
Ghina'a I. Abu Deiab, Mohammed H. Al-Huniti, I. F. Dempsey Hyatt, Emma E. Nagy, Kristen E. Gettys, Sommayah S. Sayed, Christine M. Joliat, Paige E. Daniel, Rupa M. Vummalaneni, Andrew T. Morehead, Andrew L. Sargent, Mitchell P. Croatt
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2017)