Reactions of aliphatic fluoro-alcohols with CHClF2 at atmospheric pressure

Mizukado, Junji; Matsukawa, Yasuhisa; Quan, Hengdao; Tamura, Masanori; Sekiya, Akira

doi:10.1016/j.jfluchem.2005.12.034

Cited by 17 publications

(8 citation statements)

References 10 publications

(13 reference statements)

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“…Fluorinated alcohols,214f, 215 quinoxalinones,216 as well as amides and oximes217 can undergo O ‐difluoromethylation with various difluoromethylating reagents. Nonfluorinated aliphatic alcohols remain problematic substrates for difluoromethylation and often give rise to low yields 218.…”

Section: Difluoromethylationmentioning

confidence: 99%

Introduction of Fluorine and Fluorine‐Containing Functional Groups

Liang¹,

Neumann²,

Ritter³

2013

Angew Chem Int Ed

2,267

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: Difluoromethylationmentioning

confidence: 99%

Introduction of Fluorine and Fluorine‐Containing Functional Groups

Liang¹,

Neumann²,

Ritter³

2013

Angew Chem Int Ed

2,267

856

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“…To access difluoromethyl ethers, [8][9][10][11] the difluoromethylation of alcohols and phenols with difluorocarbene (:CF 2 )i s af acile approach owing to the ready availability of many reagents. [10,11] However, current syntheses of difluoromethyl ethers with :CF 2 reagents mainly focus on the difluoromethylation of phenols under basic conditions; [10] the difluoromethylation of alcohols under similar reaction conditions is usually less productive as aresult of the competitive reactions caused by the base.T od ate,o nly several reagents,i ncluding HCF 2 Cl, [12] BrCF 2 P(O)(OEt) 2 , [13] and TMSCF 2 Br, [14] have been reported for difluoromethylation of alcohols under basic conditions with limited functional group compatibility (Scheme 1a,b asic). Although some methods that can avoid strongly basic conditions by the use of special :CF 2 reagents, such as CF 2 N 2 , [15] HFPO, [16] and CF 3 ZnBr·2 CH 3 CN, [17] have been exploited for alcohol difluoromethylation, these methods usually require excess amounts of alcohols and suffer from narrow substrate scope (Scheme 1a,neutral).…”

mentioning

confidence: 99%

Efficient Difluoromethylation of Alcohols Using TMSCF₂Br as a Unique and Practical Difluorocarbene Reagent under Mild Conditions

et al. 2017

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A general method for the efficient difluoromethylation of alcohols using commercially available TMSCF Br (TMS=trimethylsilyl) as a unique and practical difluorocarbene source is developed. This method allows primary, secondary, and even tertiary alkyl difluoromethyl ethers to be synthesized under weakly basic or acidic conditions. The reaction mainly proceeds through the direct interaction between a neutral alcohol and difluorocarbene, which is different from the difluoromethylation of phenols. Moreover, alcohols containing other moieties that are also reactive toward difluorocarbene can be transformed divergently by using TMSCF Br. This research not only solves the synthetic problem of difluorocarbene-mediated difluoromethylation of alcohols, it also provides new insights into the different reaction mechanisms of alcohol difluoromethylation and phenol difluoromethylation with difluorocarbene species.

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“…目前, 对于二氟甲基醚的制备, 大多通过酚或醇与二氟卡宾(:CF 2 )的反应来实现. 可以制备:CF 2 的试剂主要有 HCF 2 Cl [9] 、BrCF 2 P(O)(OEt) 2 [10] 、TMSCF 2 Br [11] 、 HFPO [12] 、CF 3 ZnBr•2CH 3 CN [13] 、FSO 2 CF 2 CO 2 H [14] [16] .…”

Section: 基于羟基的二氟甲基醚(R-ocf 2 H)的制备unclassified