Why Does Rh Prefer [4 + 1] while Pd Prefer [4 + 4 + 1] Mode in Carbocyclization of Vinylallene with CO? Unveiling Nickel’s Potential for Expanding the Scope Beyond Pd DOI

Sheetal Ranaut,

Shivnath Mazumder

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 14, 2025

Rhodium(I) promotes a [4 + 1] assembly mode with vinylallene substrate and CO, leading to the formation of five-membered ring structure. In striking contrast, palladium(0) catalyzes more complex 4 nine-membered cyclic ketone. The underlying mechanisms that govern this contrast in modes remain unclear, even today's date, presenting major challenge further development efficient reactions. Our computational study reveals Rh adopts square pyramidal geometry CO. This is Pd, which prefers trigonal planar geometry. A stronger metal-CO interaction detected than Pd intermediate, making preferable Pd. transition state for C-C coupling between two has significantly distorted tetrahedral core case Rh, while retains stable structure, reaction less favorable By conceptualizing transferring critical features Ni systems, we have rationally designed Ni-catalyzed version combines desirable reactivity cost-effectiveness abundance Ni, aligning growing demand sustainable atom-efficient strategies synthetic organic chemistry.

Language: Английский

Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications DOI Creative Commons
Xiaopeng Peng, Abdur Rahim, Weijie Peng

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(4), P. 1364 - 1416

Published: Jan. 17, 2023

Hypervalent aryliodoumiums are intensively investigated as arylating agents. They excellent surrogates to aryl halides, and moreover they exhibit better reactivity, which allows the corresponding arylation reactions be performed under mild conditions. In past decades, acyclic aryliodoniums widely explored However, unmet need for is improvement of their notoriously low reaction economy because coproduced iodides during often wasted. Cyclic have intrinsic advantage in terms economy, started receive considerable attention due valuable synthetic applications initiate cascade reactions, can enable construction complex structures, including polycycles with potential pharmaceutical functional properties. Here, we summarizing recent advances made research field cyclic aryliodoniums, nascent design aryliodonium species applications. First, general preparation typical diphenyl iodoniums described, followed by heterocyclic monoaryl iodoniums. Then, initiated arylations coupled subsequent domino summarized construct polycycles. Meanwhile, building biaryls axial atropisomers discussed a systematic manner. Finally, very advance employed halogen-bonding organocatalysts described.

Language: Английский

Citations

71
Enantioselective Transformations in the Synthesis of Therapeutic Agents DOI
Yang He,

Hanxiao Yu,

I. Stolarzewicz

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(15), P. 9397 - 9446

Published: July 7, 2023

The proportion of approved chiral drugs and drug candidates under medical studies has surged dramatically over the past two decades. As a consequence, efficient synthesis enantiopure pharmaceuticals or their synthetic intermediates poses profound challenge to medicinal process chemists. significant advancement in asymmetric catalysis provided an effective reliable solution this challenge. successful application transition metal catalysis, organocatalysis, biocatalysis pharmaceutical industries promoted discovery by precise preparation enantio-enriched therapeutic agents, facilitated industrial production active ingredient economic environmentally friendly fashion. present review summarizes most recent applications (2008–2022) industry ranging from scales pilot levels. It also showcases latest achievements trends agents with state art technologies catalysis.

Language: Английский

Citations

43
Recent advances in hydride transfer-involved C(sp3)–H activation reactions DOI
Xiao‐De An, Jian Xiao

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(6), P. 1364 - 1383

Published: Jan. 1, 2021

This review summarizes the recent progresses (2016–2020) in hydride transfer-enabled C(sp3)–H activation according to reaction types, categorized into intramolecular/intermolecular functionalization, and reduction.

Language: Английский

Citations

87
Regiodivergent Synthesis of Spirocyclic Compounds through Pd‐Catalyzed Regio‐ and Enantioselective [3+2] Spiroannulation DOI
Barry M. Trost, Zhijun Zuo

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(11), P. 5806 - 5810

Published: Jan. 21, 2021

Abstract A novel Pd 0 ‐catalyzed highly regio‐ and enantioselective [3+2] spiroannulation reaction has been developed for rapid assembly of a new class [5,5] spirocyclic carbo‐ heterocycles. Notably, the regioselectivity could be dominated by fine‐tuning Pd‐π‐allyl intermediate. An array coupling partners well‐tolerated with excellent regio‐, enantioselectivities. Moreover, potential application this was exemplified several further transformations.

Language: Английский

Citations

72
Advances in Palladium‐Catalyzed Decarboxylative Cycloadditions of Cyclic Carbonates, Carbamates and Lactones DOI
Yong You, Qun Li, Yanping Zhang

et al.

ChemCatChem, Journal Year: 2022, Volume and Issue: 14(9)

Published: Jan. 31, 2022

Abstract Palladium‐catalyzed decarboxylative cycloadditions have emerged as highly effective methods for constructing structurally diverse carbo‐ and heterocycles because of the formation at least two carbon‐carbon or carbon‐heteroatom bonds in a single step. It is great interest to chemists that this type cycloaddition reactions possesses some special advantages such high reactivity, exclusive regioselectivity, good functional group compatibility. Based on these qualities, palladium‐catalyzed present strong ability synthetic chemistry been flourished especially last five years. In review, achievements involving cyclic carbonates, carbamates, lactones accessing oxacyclo‐, azacyclo‐ carbocyclic compounds are addressed. Mechanistic insights applications toward synthesis natural products discussed. The challenges opportunities field also outlined.

Language: Английский

Citations

70
K2S2O8/I2-Promoted Electrophilic Selenylative Cyclization To Access Seleno-Benzo[b]azepines DOI
Zhen Zhang, Shilong Wang,

Pengpeng Tan

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(12), P. 2288 - 2293

Published: March 23, 2022

A novel and simple organoselenium-involved 7-membered cyclization to access diverse seleno-benzo[b]azepines has been developed. This protocol involves an electrophilic process is accomplished under mild conditions. Discussion of the mechanism rationalizes regioselectivity observed in transformation. The studies further transformation large-scale experiment reveal promising utility this methodology.

Language: Английский

Citations

46
Visible-Light-Promoted Selective Sulfonylation and Selenylation of Dienes to Access Sulfonyl-/Seleno-benzazepine Derivatives DOI
Zhen Zhang,

Pengpeng Tan,

Shilong Wang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(22), P. 4208 - 4213

Published: May 30, 2023

A novel visible-light-promoted selective sulfonylation and selenylation of dienes with selenosulfonates has been developed. This technology provides mild access to a wide range sulfonyl benzo[b]azepinones seleno-benzo[b]azepines. Preliminary mechanistic studies suggest that the involves radical engaged cascade process, is accomplished through sequential oxidation/electrophilic cyclization process. The large-scale operation late-stage modification experiment reveal promising utility this protocol.

Language: Английский

Citations

38
Recent advances in the total synthesis of natural products bearing the contiguous all-carbon quaternary stereocenters DOI

Zhengyuan Xin,

Hui Wang, Haibing He

et al.

Tetrahedron Letters, Journal Year: 2021, Volume and Issue: 71, P. 153029 - 153029

Published: March 27, 2021

Language: Английский

Citations

48
Asymmetric Total Synthesis of Twin Bufogargarizins A and B DOI
Liping Zhong, Rui Feng, Jingjing Wang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(4), P. 2098 - 2103

Published: Jan. 19, 2023

The first and asymmetric total synthesis of bufogargarizins A B, two unusual highly oxygenated twin steroids with rearranged A/B rings, was achieved. synthetically challenging [7–5–6–5] tetracyclic ring system bufogargarizin efficiently constructed by the intramolecular Ru-catalyzed [5 + 2] cycloaddition reaction a vinyl ether cyclopropane-yne. Notably, interesting [5–7–6–5] skeleton B diastereoselectively reassembled unique retro-aldol/transannular aldol cascade reactions from framework.

Language: Английский

Citations

21
Photo- or Electrochemical Cyclization of Dienes with Diselenides to Access Seleno-Benzo[b]azepines DOI

Pengpeng Tan,

Liwang Lu,

Shilong Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(11), P. 7245 - 7255

Published: May 23, 2023

A cascade selenylation/cyclization of dienes with diselenides has been realized under visible-light irradiation or electrolysis conditions. Employing O2 electricity as a "green" oxidant, this protocol provides green and efficient method for an array biologically important seleno-benzo[b]azepine derivatives in moderate to good yields. The direct sunlight gram-scale reaction render the approach practical attractive.

Language: Английский

Citations

18