A Novel, Practical Synthesis of Estra-1,3,5(10)-triene-3,17.beta.-dicarboxylic Acid 17-tert-Butylamide (SK&amp;F 105656) from Estrone, via a Palladium-Catalyzed Methoxycarbonylation of a 3-Fluorosulfonate

McGuire, Michael A.; Sorenson, E.; Owings, F. W.; Resnick, T.; FOX, M. J.; Baine, Neil H.

doi:10.1021/jo00101a028

Cited by 37 publications

(14 citation statements)

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“…[134] A dramatic illustration of the utility of fluorosulfate as an inexpensive triflate alternative was later provided by a process developed by SmithKline Beecham chemists. [136] Fluorosulfate prepared from the corresponding phenol and fluorosulfonic acid anhydride, the most common procedure at the time, engaged in efficient palladium catalyzed methoxycarbonylation on a 50-gallon scale.…”

Section: Methodsmentioning

confidence: 99%

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

et al. 2014

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Aryl sulfonyl chlorides (e.g. Ts-Cl) are beloved of organic chemists as the most commonly used S(VI) electrophiles, and the parent sulfuryl chloride, O2 S(VI) Cl2 , has also been relied on to create sulfates and sulfamides. However, the desired halide substitution event is often defeated by destruction of the sulfur electrophile because the S(VI) Cl bond is exceedingly sensitive to reductive collapse yielding S(IV) species and Cl(-) . Fortunately, the use of sulfur(VI) fluorides (e.g., R-SO2 -F and SO2 F2 ) leaves only the substitution pathway open. As with most of click chemistry, many essential features of sulfur(VI) fluoride reactivity were discovered long ago in Germany.6a Surprisingly, this extraordinary work faded from view rather abruptly in the mid-20th century. Here we seek to revive it, along with John Hyatt's unnoticed 1979 full paper exposition on CH2 CH-SO2 -F, the most perfect Michael acceptor ever found.98 To this history we add several new observations, including that the otherwise very stable gas SO2 F2 has excellent reactivity under the right circumstances. We also show that proton or silicon centers can activate the exchange of SF bonds for SO bonds to make functional products, and that the sulfate connector is surprisingly stable toward hydrolysis. Applications of this controllable ligation chemistry to small molecules, polymers, and biomolecules are discussed.

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Section: Methodsmentioning

confidence: 99%

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

et al. 2014

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“…[29,30] Fluorosulfonates, also known as "super sulfates," were first reported more than four decades ago, [31][32][33][34][35][36] their chemistry, however, is relatively unexplored. [29,30] Fluorosulfonates, also known as "super sulfates," were first reported more than four decades ago, [31][32][33][34][35][36] their chemistry, however, is relatively unexplored.…”

Section: Introductionmentioning

confidence: 99%

DNA‐Encoded Libraries: Aryl Fluorosulfonates as Versatile Electrophiles Enabling Facile On‐DNA Suzuki, Sonogashira, and Buchwald Reactions

Wang

et al. 2019

Advanced Science

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are encoded by unique DNA sequences as identification "barcodes," and are assembled combinatorial using split-andpool strategy or alternative procedures via DNA-compatible reactions. [7][8][9] DELs comprising millions or even billions of DNA-tagged druglike molecules can be effectively synthesized via this technology and screened against various protein targets of interest in a single pooled assay. In a typical affinity-based selection experiment, when non-and low-affinity binders are washed away, the DNA tag of the remaining compounds can be amplified using polymerase chain reaction and the relative frequency of the remaining compounds before and after selection is determined by counting the number of DNA tags in high-throughput DNA sequencing experiments. [10,11] To date, a large number of high-quality hits have been identified by the DEL technology for various therapeutically relevant targets, such as kinases, [12] phosphatases, [13] and G-protein coupled receptors. [14] Several drug candidates derived from their corresponding DEL hits, such as soluble epoxide hydrolase inhibitor GSK2256294, and death domain receptor-associated adaptor kinase RIP1 inhibitor GSK2982772 have progressed to latestage clinical development, [15,16] further emphasizing DEL as a powerful technology for small molecular drug discovery.Despite these successes, the great potential of DEL technology in drug discovery has not yet been fully realized. One of the most fundamental challenges is the synthesis of high-quality libraries with more structural diversity, which in turn depends on the development of new and robust DNA-compatible reactions that allow more flexibility in DEL's design and synthesis. Among various DNA-compatible reactions developed in recent years, transition-metal-promoted reactions such as Suzuki-Miyaura coupling, [17][18][19][20][21][22][23] Sonogashira coupling, and Buchwald-Hartwig amination using DNA-conjugated aryl halides as electrophiles have been elegantly developed (Figure 1), [24][25][26] and some of them have been developed for DEL synthesis. However, the environmental toxicity and high costs of aryl halides have hindered their large-scale applications in industry. Thus, much attention has been paid to phenol-derived electrophiles recently, [27] which, as compared to aryl halides, offer a more sustainable starting material because most of them are readily available from biomass. [28] In addition, phenol modules are also important components of natural products (NPs), bioactive molecules, and pharmaceutical drugs. Coupling reactions with Using (hetero)aryl fluorosulfonates as versatile electrophiles, facile on-DNA cross-coupling reactions of Suzuki, Sonogashira, and Buchwald are reported here. Notably, all of these reactions show excellent functional group tolerance, mild reaction conditions (relative low temperature and open to air), rich heterocyclic coupling partners, and more importantly, DNA-compatibility. Thus, these new reactions based on efficient formation of C(sp 2 )-C(sp 2 ), C(sp 2 )-C(sp), and C(s...

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“…In 1994, McGuire et al. reported a synthesis of aryl fluorosulfate 66 in 87 % yield from the reaction of substituted phenol 65 with fluorosulfonic anhydride in the presence of Et 3 N as a base in CH 2 Cl 2 (Scheme ) . Owing to the commercial unavailability of fluorosulfonic anhydride, the fluorosulfonation of compound 65 was complicated.…”

Section: Synthesis Of Fluorosulfatesmentioning

confidence: 99%

“…A theatrical illustration of the utility of fluorosulfate as an economical alternative to triflate was later provided by chemists at SmithKline Beecham . Fluorosulfates that were synthesized from the corresponding phenol and fluorosulfonic acid anhydride, the well‐known procedure at the time, were utilized in a palladium‐catalyzed methoxycarbonylation reaction on a 50‐gallon scale.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Chemical Transformations of Fluorosulfates

Lekkala

Leng

et al. 2018

Asian J Org Chem

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Fluorosulfates are readilya vailablee lectrophiles that can be prepared from the reactions of phenol or alcohol derivatives with sulfuryl fluoride, fluorosulfonic acid, sulfuryl chloridef luoride, and fluorosulfonic anhydride. This Focus Review coversm ost of the synthetic strategies that have been reported for the construction of fluorosulfates,a s well as their application as versatile buildingb locks in av ariety of synthetic transformations, such as catalyzed amination, cross-coupling, sulfur(VI) fluoridee xchange, carbonylation, hydrolysis, alcoholysis,a nd as alternatives to organic halidesort riflates in organic chemistry.Scheme79. Synthesis of g-pyrone by using fluorosulfate 34.Scheme80. Reactions of fluorosulfatesw ith nucleophilicreagents.Scheme81. Synthesis of the desired allenefrom fluorosulfate 68. Scheme82. Preparation of benzenef rom phenyl fluorosulfate (110).Scheme83. Synthesis of compound 170 from fluorosulfate 169.

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A Novel, Practical Synthesis of Estra-1,3,5(10)-triene-3,17.beta.-dicarboxylic Acid 17-tert-Butylamide (SK&F 105656) from Estrone, via a Palladium-Catalyzed Methoxycarbonylation of a 3-Fluorosulfonate

Cited by 37 publications

References 0 publications

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

DNA‐Encoded Libraries: Aryl Fluorosulfonates as Versatile Electrophiles Enabling Facile On‐DNA Suzuki, Sonogashira, and Buchwald Reactions

Synthesis and Chemical Transformations of Fluorosulfates

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