Reactions of allyl alcohols and boronic acids with trifluoromethanesulfonyl hypervalent iodonium ylide under copper-catalysis

Arimori, Sadayuki; Takada, Masahiro; Shibata, Norio

doi:10.1039/c5dt02214b

Cited by 55 publications

(12 citation statements)

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“…Incidentally, we reported in 2013 that trifluoromethanesulfonyl (SO 2 CF 3 ) hypervalent iodonium ylide 1 is an efficient reagent for the electrophilic trifluoromethylthiolation reaction ( figure 1 b ) [ 62 ]. Despite its carbon-SO 2 CF 3 structure, a reactive SCF 3 species is unexpectedly, but effectively released from 1 via C–S bond cleavage under copper catalysis allowing it to be transferred into a wide variety of nucleophilic substrates including enamines, indoles, β-keto esters, pyrroles [ 63 ], allylsilanes, silyl enol ethers [ 64 ], allyl alcohols and boronic acids [ 65 ]. Inspired by this powerful reactivity and wide substrate generality and linked to the mechanistic uniqueness of iodonium ylide reagent 1 , we describe herein an investigation of novel shelf-stable electrophilic difluoromethylthiolation reagents 2 and their reactivity towards a variety of nucleophiles ( figure 1 c ).…”

Section: Introductionmentioning

confidence: 99%

Difluoromethanesulfonyl hypervalent iodonium ylides for electrophilic difluoromethylthiolation reactions under copper catalysis

et al. 2016

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Difluoromethanesulfonyl hypervalent iodonium ylides 2 were developed as electrophilic difluoromethylthiolation reagents for a wide range of nucleophiles. Enamines, indoles, β-keto esters, silyl enol ethers and pyrroles were effectively reacted with 2 affording desired difluoromethylthio (SCF2H)-substituted compounds in good to high yields under copper catalysis. The reaction of allyl alcohols with 2 under the same conditions provided difluoromethylsulfinyl (S(O)CF2H) products in good yields. The difluoromethylthiolation of enamines is particularly effective with wide generality, thus the enamine method was nicely extended to the synthesis of a series of difluoromethythiolated cyclic and acyclic β-keto esters, 1,3-diketones, pyrazole and pyrimidine derivatives by a consecutive, two-step one-pot reaction using 2.

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Section: Introductionmentioning

confidence: 99%

Difluoromethanesulfonyl hypervalent iodonium ylides for electrophilic difluoromethylthiolation reactions under copper catalysis

et al. 2016

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“…[94] . 随后, 他们利用该试剂, 也实现了铜催化下硼酸 [95] 、芳胺 [96] 、吡咯 [97] 、烯丙基硅 [98] 、烯醇硅醚 [98] 的亲电三氟甲硫基化反应. 对于烯丙醇的底物, 他们也同样采用该试剂, 可以实现重排反应 [95] (Scheme 45).…”

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Recent Progress on Direct Trifluoromethylthiolating Reagents and Methods

Zhang¹,

Lü²,

Shen³

2017

Acta Chim. Sinica

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With a significantly high Hansch's hydrophobicity parameter (π＝1.44), electron-withdrawing trifluoromethylthio group (CF 3 S-) has been considered as one of the most lipophilic substituents and privileged fragments that are able to improve drug molecules' pharmacokinetic and physicochemical properties such as lipophilicity and metabolic stability. It is well-known that incorporation of the trifluoromethylthio group into small molecules greatly enhances its ability to cross lipid membranes and in vivo absorpotion rate. In addition, the high electronegativity of the trifluoromethylthio group significantly improves the small molecule's stablity in acidic environments. Not surprisingly, the trifluoromethylthio group has been of special attention not only from the academia but also from pharmaceutical and agrochemical industry for their use in isostere-based drug design. Development of highly efficient methods for the introduction of the trifluoromethylthio group into small molecules, thereafter, has become a subject of recent focus in the field of organic chemistry. In the early 1960s, a few methods for the formation of trifluoromethylthioethers were reported, which typically involved halogen exchange of the trichloromethyl-substituted compounds and trifluoromethylation of thiolated substrates. However, the conditions of these methods were harsh and incompatible with many common functional groups. Since 2008, new reagents and methods that were able to efficiently incorporate the trifluoromethylthio group under mild conditions have emerged, that pave the way for the facile introduction of trifluoromethylthio group into site-specific positions of the target molecules. In this review, we will first briefly introduce the indirect strategies for trifluoromethylthiolation including halogen exchange and trifluoromethylation of thiolated substrates, and then focus on the direct trifluoromethylthiolation strategies including the transition metal-catalyzed trifluoromethylthiolation reactions, electrophilic trifluoromethylthiolation reactions with electrophilic trifluoromethylthiolating reagents and radical trifluoromethylthiolations. These methods represent the most straightforward and promising approaches for the incorporation of the trifluoromethylthio group into small molecules. At the end, we will discuss the remaining problems and challenges in this particular field.

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“…Since the initial report of N ‐trifluoromethylthiophthalimide by Munavalli, several shelf‐stable reagents have been reported, including trifluoromethanesulfenamide reagents (Billard, 2008), a trifluoromethylthio‐ether reagent (Shen, 2013), and trifluoromethylthio saccharine (Shen, 2014) . In 2013, we disclosed trifluoromethanesulfonyl hypervalent iodonium ylide 1 as a novel, shelf‐stable reagent for the electrophilic trifluoromethylthiolation of enamines, indoles, and β‐keto ester, and the utility of 1 was greatly expanded to the functionalization of pyrroles, allylsilanes and silyl enol ethers, arylamines, boronic acids, and allylic alcohols (Figure ) . Even though 1 is a trifluoromethanesulfonyl (SO 2 CF 3 ) compound, it effectively releases electrophilic SCF 3 species via carbene generation.…”

Section: Figurementioning

confidence: 97%

2‐Diazo‐1‐phenyl‐2‐((trifluoromethyl)sulfonyl)ethan‐1‐one: Another Utility for Electrophilic Trifluoromethylthiolation Reactions

et al. 2016

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Abstract2‐Diazo‐1‐phenyl‐2‐((trifluoromethyl)sulfonyl)ethan‐1‐one (diazo‐triflone) (2) is not only a building block but also a reagent. In this study, diazo‐triflone, which was originally used for the synthesis of β‐lactam triflones as a trifluoromethanesulfonyl (SO2CF3) building block under catalyst‐free thermal conditions, is redisclosed as an effective electrophilic trifluoromethylthiolation reagent under copper catalysis. A broad set of enamines, indoles, β‐keto esters, pyrroles, and anilines were nicely transformed into corresponding trifluoromethylthio (SCF3) compounds in good to high yields by diazo‐triflone under copper catalysis via an electrophilic‐type reaction. A coupling‐type trifluoromethylthiolation reaction of aryl iodides was also realized by diazo‐triflone in acceptable yields.

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Reactions of allyl alcohols and boronic acids with trifluoromethanesulfonyl hypervalent iodonium ylide under copper-catalysis

Cited by 55 publications

References 62 publications

Difluoromethanesulfonyl hypervalent iodonium ylides for electrophilic difluoromethylthiolation reactions under copper catalysis

Difluoromethanesulfonyl hypervalent iodonium ylides for electrophilic difluoromethylthiolation reactions under copper catalysis

Recent Progress on Direct Trifluoromethylthiolating Reagents and Methods

2‐Diazo‐1‐phenyl‐2‐((trifluoromethyl)sulfonyl)ethan‐1‐one: Another Utility for Electrophilic Trifluoromethylthiolation Reactions

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