A novel synthesis of functionalized 1,1-difluoro-1-alkenes via isolable 2,2-difluorovinylsilanes

Ichikawa, Junji; Ishibashi, Yuichiro; Fukui, Hirokazu

doi:10.1016/s0040-4039(02)02652-7

Cited by 50 publications

(14 citation statements)

References 23 publications

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“…Geminally substituted trifluoromethyldimethylphenylsilyl alkenes can be transformed to the 1,1‐difluoroalkenes by the S N 2′ addition of various nucleophiles. such as LAH, organolithium reagents, and lithium enolates (Scheme ) 527. Similarly, trifluoromethylstyrene derivatives can rearrange to geminal difluoroalkenyl amines528 after the addition of lithium amide or allylic alkyl difluoroalkenes529 or organolithium reagents (Scheme ).…”

Section: Fluorinated Alkenesmentioning

confidence: 99%

Introduction of Fluorine and Fluorine‐Containing Functional Groups

Liang¹,

Neumann²,

Ritter³

2013

Angew Chem Int Ed

2,266

856

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Over the past decade, the most significant, conceptual advances in the field of fluorination were enabled most prominently by organo‐ and transition‐metal catalysis. The most challenging transformation remains the formation of the parent CF bond, primarily as a consequence of the high hydration energy of fluoride, strong metal—fluorine bonds, and highly polarized bonds to fluorine. Most fluorination reactions still lack generality, predictability, and cost‐efficiency. Despite all current limitations, modern fluorination methods have made fluorinated molecules more readily available than ever before and have begun to have an impact on research areas that do not require large amounts of material, such as drug discovery and positron emission tomography. This Review gives a brief summary of conventional fluorination reactions, including those reactions that introduce fluorinated functional groups, and focuses on modern developments in the field.

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Section: Fluorinated Alkenesmentioning

confidence: 99%

Introduction of Fluorine and Fluorine‐Containing Functional Groups

Liang¹,

Neumann²,

Ritter³

2013

Angew Chem Int Ed

2,266

856

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“…It was reported that difluoroalkenes 10 c and 10 f were prepared in 56 and 45 % overall yield, respectively, by a two‐step palladium‐catalyzed cross‐coupling reaction from 2,2‐difluoro‐1‐tributylstannylethenyl p ‐toluenesulfonate;8e by our method, 10 c and 10 f were obtained in 83 and 69 % yield, respectively (Table 2, entries 3 and 9). gem ‐Difluoroalkene 10 m , which is difficult to prepare by palladium‐catalyzed transformation due to the inevitable CBr bond cleavage by Pd 0 ,8f–h was prepared in 77 % yield from the readily available ketone 9 m . The reaction conditions also worked well with some heteroaryl ketones.…”

Section: Resultsmentioning

confidence: 99%

gem‐Difluoroolefination of Diaryl Ketones and Enolizable Aldehydes with Difluoromethyl 2‐Pyridyl Sulfone: New Insights into the Julia–Kocienski Reaction

Gao

Zhao

et al. 2014

Chemistry A European J

107

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The direct conversion of diaryl ketones and enolizable aliphatic aldehydes into gem-difluoroalkenes has been a long-standing challenge in organofluorine chemistry. Herein, we report efficient strategies to tackle this problem by using difluoromethyl 2-pyridyl sulfone as a general gem-difluoroolefination reagent. The gem-difluoroolefination of diaryl ketones proceeds by acid-promoted Smiles rearrangement of the carbinol intermediate; the gem-difluoroolefination is otherwise difficult to achieve through a conventional Julia-Kocienski olefination protocol under basic conditions due to the retro-aldol type decomposition of the key intermediate. Efficient gem-difluoroolefination of aliphatic aldehydes was achieved by the use of an amide base generated in situ (from CsF and tris(trimethylsilyl)amine), which diminishes the undesired enolization of aliphatic aldehydes and provides a powerful synthetic method for chemoselective gem-difluoroolefination of multi-carbonyl compounds. Our results provide new insights into the mechanistic understanding of the classical Julia-Kocienski reaction.

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“…This method has also been applied to the synthesis of divinyl ketones bearing vinylic trifluoromethyl groups as Nazarov substrates [30] . In addition, the synthesis of 1‐trifluoromethylvinylsilane reported by Ichikawa's group, which was only applied to S N 2’ reaction with nucleophiles to construct 2,2‐difluorovinylsilanes [31] …”

Section: Cross‐coupling Reactionsmentioning

confidence: 99%

2‐Bromo‐3,3,3‐Trifluoropropene: A Versatile Reagent for the Synthesis of Fluorinated Compounds

2022

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2‐Bromo‐3,3,3‐trifluoropropene (BTP) represents a highly valuable synthon in synthetic chemistry, and has been widely used in organic synthesis, mainly including addition reactions, cross‐coupling reactions, cycloaddition or cyclization reactions, SN2’ reactions, and Stetter reactions for the construction of various fluorinated organic compounds. In this review, we systematically summarize these reactions; their mechanisms are also discussed.

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A novel synthesis of functionalized 1,1-difluoro-1-alkenes via isolable 2,2-difluorovinylsilanes

Cited by 50 publications

References 23 publications

Introduction of Fluorine and Fluorine‐Containing Functional Groups

Introduction of Fluorine and Fluorine‐Containing Functional Groups

gem‐Difluoroolefination of Diaryl Ketones and Enolizable Aldehydes with Difluoromethyl 2‐Pyridyl Sulfone: New Insights into the Julia–Kocienski Reaction

2‐Bromo‐3,3,3‐Trifluoropropene: A Versatile Reagent for the Synthesis of Fluorinated Compounds

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