Controlling Reactivity and Selectivity in the Mizoroki-Heck Reaction: High Throughput Evaluation of 1,5-Diaza-3,7-diphosphacyclooctane Ligands DOI Creative Commons
Eric S. Isbrandt,

Devon E. Chapple,

Nguyễn Thiên Phúc Từ

и другие.

Опубликована: Дек. 22, 2023

We report a high throughput evaluation of the Mizoroki-Heck reaction diverse olefin coupling partners. Comparison different ligands revealed 1,5-diaza-3,7-diphosphacyclooctane (P2N2) scaffold to be more broadly applicable than common ‘gold standard’ ligands, demonstrating that this family readily accessible diphosphines have unrecognized potential in organic synthesis. In particular, two structurally related P2N2 were identified enable regiodivergent arylation styrenes. By simply altering phosphorus substituent from phenyl tert-butyl group, both linear and branched products can obtained regioisomeric ratios. Experimental computational mechanistic studies performed further probe origin selectivity, which suggests coordinate metal similar manner, but rigid positioning forces contact with incoming pi-pi interaction (for P-Ph ligands) or steric clash P-tBu ligands), dictating regiocontrol

Язык: Английский

Controlling Reactivity and Selectivity in the Mizoroki–Heck Reaction: High Throughput Evaluation of 1,5-Diaza-3,7-diphosphacyclooctane Ligands DOI
Eric S. Isbrandt,

Devon E. Chapple,

Nguyễn Thiên Phúc Từ

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5650 - 5660

Опубликована: Фев. 15, 2024

We report a high throughput evaluation of the Mizoroki–Heck reaction diverse olefin coupling partners. Comparison different ligands revealed 1,5-diaza-3,7-diphosphacyclooctane (P2N2) scaffold to be more broadly applicable than common "gold standard" ligands, demonstrating that this family readily accessible diphosphines has unrecognized potential in organic synthesis. In particular, two structurally related P2N2 were identified enable regiodivergent arylation styrenes. By simply altering phosphorus substituent from phenyl tert-butyl group, both linear and branched products can obtained regioisomeric ratios. Experimental computational mechanistic studies performed further probe origin selectivity, which suggests coordinate metal similar manner but rigid positioning forces contact with incoming π–π interaction (for P-Ph ligands) or steric clash P-tBu ligands), dictating regiocontrol.

Язык: Английский

Процитировано

6
Synthesis of naphthalene derivatives via nitrogen-to-carbon transmutation of isoquinolines DOI Creative Commons

Tongtong Zhu,

Xiang Cui, Wenjun Ma

и другие.

Science Advances, Год журнала: 2025, Номер 11(5)

Опубликована: Янв. 29, 2025

Heteroarene skeletal editing is gaining popularity in synthetic chemistry. Transmuting single atoms generates molecules that have distinctly varied properties, thereby fostering potent molecular exchanges can be extensively used to synthesize functional molecules. Herein, we present a convenient protocol for nitrogen-carbon single-atom transmutations isoquinolines, which inspired by the Wittig reaction and enables easy access substituted naphthalene derivatives. The uses an inexpensive commercially available phosphonium ylide as carbon source furnish wide range of naphthalenes. key success this transformation formation triene intermediate through ring opening, undergoes 6π-electrocyclization elimination processes afford product. Furthermore, strategy facile synthesis 13 C-labeled naphthalenes using CH 3 PPh I commercial C facilitates modifying directing group C─H functionalization.

Язык: Английский

Процитировано

0
Multimodal Precise Control Over Multiselective Carbonylation of 1,3-Enynes DOI Creative Commons
Chang‐Sheng Kuai, Yuanrui Wang, Ting Yang

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(9), С. 7950 - 7964

Опубликована: Фев. 19, 2025

Efficiently constructing structurally diverse and complex organic molecules through selective catalytic functionalization is a central goal in synthetic chemistry, yet achieving precise control over multiple reactive centers multisite substrates remains formidable challenge. Building on foundational advances single- dual-selective transformations, we report multimodal strategy for the carbonylation of 1,3-enynes, versatile class substrates. Through meticulous fine-tuning conditions, our approach enables five distinct regio- stereoselective carbonylative including direct (1,2- 2,1-hydroaminocarbonylation) tandem cyclization pathways (2,4-, 1,3-, 2,3-carbonylation). Furthermore, mechanistic studies suggested that multidimensional regulation seamless relay up to three reactions (hydroaminocarbonylation-hydroamination-transamination) with exceptional accuracy. This unified platform not only establishes robust framework tackling enduring challenges selectivity but also broadens chemical space accessible 1,3-enyne exemplifying atom- step-economic principles paving way transformative advancements drug discovery, materials science, beyond.

Язык: Английский

Процитировано

0
Recent Advances in Nonprecious Metal Catalysis DOI
Archita Sripada, Eugene Chong, Hao Wu

и другие.

Organic Process Research & Development, Год журнала: 2024, Номер 28(9), С. 3524 - 3544

Опубликована: Авг. 9, 2024

Developing catalytic reactions using nonprecious-metal to achieve various synthetic transformations remains a valuable pursuit the scientific community. As part of continuing review series that is published within precompetitive chemistry alliance between AbbVie, Boehringer Ingelheim and Pfizer, this article underscores wide-ranging uses Cu-, Co-, Fe-, Ni-catalysis. The significant uptick in NPMC-related publications signifies escalating curiosity among researchers investigate advance capabilities these metals.

Язык: Английский

Процитировано

1
Controlling Reactivity and Selectivity in the Mizoroki-Heck Reaction: High Throughput Evaluation of 1,5-Diaza-3,7-diphosphacyclooctane Ligands DOI Creative Commons
Eric S. Isbrandt,

Devon E. Chapple,

Nguyễn Thiên Phúc Từ

и другие.

Опубликована: Дек. 22, 2023

We report a high throughput evaluation of the Mizoroki-Heck reaction diverse olefin coupling partners. Comparison different ligands revealed 1,5-diaza-3,7-diphosphacyclooctane (P2N2) scaffold to be more broadly applicable than common ‘gold standard’ ligands, demonstrating that this family readily accessible diphosphines have unrecognized potential in organic synthesis. In particular, two structurally related P2N2 were identified enable regiodivergent arylation styrenes. By simply altering phosphorus substituent from phenyl tert-butyl group, both linear and branched products can obtained regioisomeric ratios. Experimental computational mechanistic studies performed further probe origin selectivity, which suggests coordinate metal similar manner, but rigid positioning forces contact with incoming pi-pi interaction (for P-Ph ligands) or steric clash P-tBu ligands), dictating regiocontrol

Язык: Английский

Процитировано

1