Iron‐Catalyzed Tandem Cyclization and Cross‐Coupling Reactions of Iodoalkanes and Aryl Grignard Reagents

Kim, Jae Gon; Son, Young Hoon; Seo, Jin Won; Kang, Eun Joo

doi:10.1002/ejoc.201403511

Cited by 26 publications

(14 citation statements)

References 72 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In 2018, the Diao group showed that a wide range of alkylbromide containing alkenes underwent intramolecular dicarbofunctionalization with a variety of (hetero)aryl and alkyl bromides (Scheme 50). [ 113 ] In contrast to the previous reports [ 114‐118 ] that the dicarbofunctionalization of alkenes was restricted to the formation of five‐membered rings, this method could afford piperidine derivatives by 6‐exo‐trig cyclization. Thorpe‐Ingold effect [ 119 ] played a crucial role on the efficiency of the radical cyclization, as the unsubstituted carbochain favored direct coupling with another electronphile, such as arylbromide, prior to cyclization.…”

Section: Intramolecular Dicarbofunctionalization Of Alkenes Via Cyclimentioning

confidence: 95%

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

2020

View full text Add to dashboard Cite

As a straightforward strategy for rapidly increasing molecular complexity, dicarbofunctionalization of alkenes has attracted substantial interests of organic synthesis, medicine chemistry, and materials science. Nickel-catalyzed cascade dicarbofunctionalizations have been flourished in this area recently, and nickel-mediated radical pathways particularly offer new opportunities in conjunctive cross-couplings with alkyl coupling partners. Herein, we give a comprehensive review of nickel-catalyzed dicarbofunctionalization of alkenes through a historical perspective, including intermolecular three-component reactions and intramolecular cascade reactions. Among the pathways discussed in this review, the carbometallation/cross-coupling process and the radical addition/cross-coupling process are the two major pathways for the nickel-catalyzed dicarbofunctionalization of alkenes. The oxidative cyclization and 1,2-metallate shift processes are also selectively discussed. These methods overcome the limitations associated with the reactions using noble metals in the field, providing an efficient and straightforward access to structurally diversified molecules. Yun-Cheng Luo (right) received his BSc degree in 2016 and master degree in 2019 from University of Science and Technology of China. Then he joined Professor Xingang Zhang's group at Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences to pursue his doctorate in organic chemistry. His research interests are focused on the activation of inert C-H or C-X bonds of bulky chemicals and their applications in the synthesis of fluorine-containing compounds. Chang Xu (middle) obtained his BSc degree in basic pharmacy from China Pharmaceutical University (China) in 2015. With an interest in organic chemistry and medicinal chemistry, he then began his graduate studies at Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences under the supervision of Professor Xingang Zhang. His research interests are focused on the activation and transformations of fluoroalkylanes and their applications in medicinal chemistry. Xingang Zhang (left) obtained his BSc degree in 1998 from Sichuan University (China) and received the Ph.D. in 2003 at Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences. After his postdoctoral work at University of Illinois at Urbana Champaign (USA), he joined the faculty team of SIOC as a research associate professor in 2008, and became research professor in 2012. His current research interests are focused on organofluorine chemistry and chemical biology.

show abstract

Section: Intramolecular Dicarbofunctionalization Of Alkenes Via Cyclimentioning

confidence: 95%

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

2020

View full text Add to dashboard Cite

show abstract

“…Another recurring motif in recent work is the direct combination of iron-catalyzed cross-coupling with other transformations to achieve cascade reactions. 23,24 A notable example of this approach is the dual use of an iron catalyst for the ring opening of a pyrone and its consecutive crosscoupling (Scheme 3). 25 Fürstner and co-workers applied this cascade reaction in the synthesis of a natural product analogue with anticancer activity.…”

Section: Short Review Syn Thesismentioning

confidence: 99%

“…The results of several radical clock and radical trap experiments are consistent with the generally accepted involvement of radicals in iron-catalyzed cross-coupling reactions of alkyl halides (also see section 3.2). 21,23,48,66,69,71 However, most of these experiments have been criticized for not being unambiguous in the case of organometallic systems. 5f Strong support for the suggested mechanism comes from the work of the Neidig group, who found the iron(II) complexes PhFeBr(SciOPP) and Ph 2 Fe(SciOPP) to react with bromocycloheptane at catalytically relevant rates.…”

Section: Scheme 14 Proposed Catalytic Fe(ii)-fe(iii) Cycle Of Iron-camentioning

confidence: 99%

Iron-Catalyzed Cross-Coupling: Mechanistic Insight for Rational Applications in Synthesis

Parchomyk

Koszinowski

2017

Synthesis

View full text Add to dashboard Cite

Iron-catalyzed cross-coupling reactions provide a promising way to form new carbon–carbon bonds and build up molecular complexity. This short review presents recent advances in the synthetic application of these reactions as well as in the elucidation of their mechanism. It also highlights remaining problems and aims at pointing out ways toward possible remedies.1 Introduction2 Synthesis: Recent Accomplishments and Unsolved Problems2.1 Substrate Scope: Electrophiles2.2 Substrate Scope: Nucleophiles2.3 Catalyst Activity and Chemoselectivity2.4 Stereoselectivity2.5 Practical Aspects3 Mechanism: Recent Insights and Open Questions3.1 Transmetallation and Activation of the Iron Precatalyst3.2 Coupling via Oxidative Addition and Reductive Elimination3.3 Coupling via C–X Bond Homolysis and Radical Rebound3.4 Coupling via Bimolecular C–X Bond Homolysis3.5 Other Reactions of Organoiron Species with Electrophiles4 Toward Rational Reaction Improvement5 Conclusion

show abstract

“…Since then, several reports of alkyl halide cross-coupling reactions have been reported [ 53 ]. In 2015, Kang and co-workers described a FeCl 2 -catalyzed tandem cyclization/cross-coupling reaction of alkyl iodides 1 with aryl Grignard reagents 2 to give arylmethyl-substituted pyrrolidines and tetrahydrofurans 3 in poor to excellent yield ( Scheme 3 ) [ 54 ].…”

Section: Reviewmentioning

confidence: 99%

Iron-catalyzed domino coupling reactions of π-systems

Pounder¹,

Tam²

2021

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

The development of environmentally benign, inexpensive, and earth-abundant metal catalysts is desirable from both an ecological and economic standpoint. Certainly, in the past couple decades, iron has become a key player in the development of sustainable coupling chemistry and has become an indispensable tool in organic synthesis. Over the last ten years, organic chemistry has witnessed substantial improvements in efficient synthesis because of domino reactions. These protocols are more atom-economic, produce less waste, and demand less time compared to a classical stepwise reaction. Although iron-catalyzed domino reactions require a mindset that differs from the more routine noble-metal, homogenous iron catalysis they bear the chance to enable coupling reactions that rival that of noble-metal-catalysis. This review provides an overview of iron-catalyzed domino coupling reactions of π-systems. The classifications and reactivity paradigms examined should assist readers and provide guidance for the design of novel domino reactions.

show abstract

Iron‐Catalyzed Tandem Cyclization and Cross‐Coupling Reactions of Iodoalkanes and Aryl Grignard Reagents

Cited by 26 publications

References 72 publications

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Iron-Catalyzed Cross-Coupling: Mechanistic Insight for Rational Applications in Synthesis

Iron-catalyzed domino coupling reactions of π-systems

Contact Info

Product

Resources

About

Iron‐Catalyzed Tandem Cyclization and Cross‐Coupling Reactions of Iodoalkanes and Aryl Grignard Reagents

Cited by 26 publications

References 72 publications

Nickel‐CatalyzedDicarbofunctionalization of Alkenes†

Nickel‐CatalyzedDicarbofunctionalization of Alkenes†

Iron-Catalyzed Cross-Coupling: Mechanistic Insight for Rational Applications in Synthesis

Iron-catalyzed domino coupling reactions of π-systems

Contact Info

Product

Resources

About

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†