A New Fluorous Methoxymethyl (<sup>F</sup>MOM) Protecting Group for Alcohols

Curran, Dennis P.; Ogoe, Claude

doi:10.1002/qsar.200640047

Cited by 16 publications

(5 citation statements)

References 22 publications

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“…In addition to the traditional role of protective groups, fluorous derivatives will facilitate the purification of protected molecules. Some representative examples of protective groups are presented in Figure 2.15 (Curran 2001;Luo et al 2001a;Luo et al 2001b;Curran and Furukawa 2002;Curran et al 2003;Curran and Ogoe 2006;Matsugi et al 2006). These protective groups have the same reactivity as their non-fluorous analogs and allow the protected compounds to be purified very effectively by FSPE.…”

Section: Example Of Application To the Synthesis Of A Group Of Amidesmentioning

confidence: 99%

Biphasic Chemistry and The Solvent Case

2020

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Fluorous tags and phases for synthesis and catalysis IntroductionThe development of more efficient, rapid and environmentally friendly synthesis processes, whether for the production of high-tonnage compounds, pharmaceutical compounds or on a laboratory scale, is an important objective of current research. Most research efforts focus on optimizing the activity of existing reagents or catalysts or discovering new reactions. However, in a synthesis process, the purification step should not be neglected, as the isolated product yield and the overall energy cost of synthesis depend strongly on the nature and efficiency of the latter (Curran 1998). Methodologies for easily separating or recycling a catalyst, reagent or by-product from a reaction medium are to be encouraged in the context of sustainable chemistry. Ideally, these methods should make it possible to avoid as much as possible chromatographic purifications that consume large amounts of organic solvents, and if possible, distillations, which are costly in terms of energy and can lead to catalyst degradation. The use of liquid (perfluorocarbons) or solid (perfluorinated silicas or Teflon) perfluorinated phases is fully in line with this approach. Perfluorocarbons (PFCs), such as n-perfluorohexane (C6F14), are liquids with extreme physicochemical properties. They are chemically inert, non-toxic and are the most non-polar liquids available. They are both hydrophobic and lipophobic, so they form liquid/liquid two-phase systems at room temperature with most organic solvents. The principle of fluorous chemistry consists of increasing the affinity of catalysts, reagents or substrates for liquid or solid perfluorinated phases, i.e. increasing their fluorophilicity. This is achieved by modifying catalysts, reagents or substrates with perfluoroalkyl fragments called fluorous tags (Ftags). As we will see later, fluorous compounds present in a reaction medium can then Chapter written by Jean-Marc VINCENT.

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Section: Example Of Application To the Synthesis Of A Group Of Amidesmentioning

confidence: 99%

Biphasic Chemistry and The Solvent Case

2020

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“…Curran and Ogoe developed a similar F-MOM 75 that has a propylene spacer (Scheme 39). 64 The protection reaction was carried out with DIPEA, and the deprotection was carried out with ZnBr 2 -BuSH or CSA.…”

Section: Alkoxyethyl and Methyloxymetyl (Mom)-type Linkersmentioning

confidence: 99%

Fluorous Linker-Facilitated Chemical Synthesis

Zhang

2009

Chem. Rev.

171

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“…Fluorous protecting groups are usually fashioned after parent (standard) protecting groups, and available protecting groups for alcohols include fluorous analogs of tetrahydropyranyl (THP),[7] p -methoxyben-zyl (PMB),[8] and methoxymethyl (MOM) groups,[9] among others. Assorted fluorous silyl groups are also available,[10] and we have often used a fluorous analog of the parent triisopropylsilyl (TIPS) group that we usually call F TIPS (Figure 1).…”

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Comparison of the Relative Reactivities of the Triisopropylsilyl Group With Two Fluorous Analogs

et al. 2009

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The relative stabilities of two fluorous analogs, diisopropyl (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silyl and diisopropyl-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecyl)silyl [C 8 F 17 (CH 2 ) n Si(i-Pr) 2 , where n = 2 or 3], of the standard triisopropylsilyl (TIPS) group are compared in the setting of alcohol protection. The fluorous silyl groups can be installed under standard conditions in comparable yields to the TIPS group, but the derived fluorous silyl ethers are more labile than TIPS ethers towards cleavage by both acids and fluoride.Keywords fluorous chemistry; protecting groups; relative reactivity; triisopropylsilyl group Fluorous protecting groups [1] have been extensively used recently in diversity-oriented synthesis, natural products synthesis and fluorous mixture synthesis. Such groups typically serve a dual role of protecting a given functional group and enabling a fluorous separation. In diversity-oriented synthesis [2] and natural products synthesis,[3] the separation method is usually a fluorous solid-phase extraction, [4] which separates fluorous components from nonfluorous ones. In fluorous mixture synthesis, [5] the method is a fluorous HPLC, [6] which resolves differentially tagged fluorous components of a mixture into individual compounds.Fluorous protecting groups are usually fashioned after parent (standard) protecting groups, and available protecting groups for alcohols include fluorous analogs of tetrahydropyranyl (THP), [7] p-methoxyben-zyl (PMB), [8] and methoxymethyl (MOM) groups,[9] among others. Assorted fluorous silyl groups are also available,[10] and we have often used a fluorous analog of the parent triisopropylsilyl (TIPS) group that we usually call F TIPS (Figure 1). [11] An understanding of the relative reactivity and stability of fluorous protecting groups is essential for synthetic planning. Fluorous groups that closely resemble the structure of their parents and that have suitable spacers can be expected to have comparable reactivities to the parent groups.[12] For example, the fluorous PMB ( F PMB) group in Figure 1 is structurally very similar to the parent PMB group, and the protected functionality is relatively well insulated from the perfluoroalkyl group (Rf) by a propylene spacer. In contrast, the parent TIPS group may not be such good model for the F TIPS group for two reasons: 1) the F TIPS group is not an analog of a triisopropylsilyl group but instead a 1°-alkyl (diisopropylsilyl) group, and 2) the ethylene spacer may not be a sufficient insulator. Thus, the F TIPS group may differ in reactivity and stability from TIPS for both steric and electronic reasons. We report here observations showing that two fluorous TIPS groups differ in reactivity from each other and from the parent TIPS group. These observations will help in selection of suitable fluorous protecting groups during synthetic planning.We first observed differences between TIPS and F TIPS groups during a fluorous mixture synthesis of a natural pro...

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A New Fluorous Methoxymethyl (^FMOM) Protecting Group for Alcohols

Cited by 16 publications

References 22 publications

Biphasic Chemistry and The Solvent Case

Biphasic Chemistry and The Solvent Case

Fluorous Linker-Facilitated Chemical Synthesis

Comparison of the Relative Reactivities of the Triisopropylsilyl Group With Two Fluorous Analogs

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A New Fluorous Methoxymethyl (FMOM) Protecting Group for Alcohols

Cited by 16 publications

References 22 publications

Biphasic Chemistry and The Solvent Case

Biphasic Chemistry and The Solvent Case

Fluorous Linker-Facilitated Chemical Synthesis

Comparison of the Relative Reactivities of the Triisopropylsilyl Group With Two Fluorous Analogs

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A New Fluorous Methoxymethyl (^FMOM) Protecting Group for Alcohols