[4+2] Cycloadditions of Seven‐Membered‐Ring trans‐Alkenes: Decreasing Reactivity with Increasing Substitution of the Seven‐Membered Ring

Santucci, John Iii; Sanzone, Jillian R.; Woerpel, K. A.

doi:10.1002/ejoc.201600329

Cited by 20 publications

(21 citation statements)

References 52 publications

(117 reference statements)

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“…37 Tomooka and Woerpel have synthesized trans -oxasilacycloalkenes, and have studied their reactivity in Diels-Alder and azide cycloadditions. 38,39 Very recently, Lemke, Kele and coworkers reported the genetic incorporation of dioxo-TCO 2 and demonstrated that the lower lipophilicity of this molecule resulted in improved washout times during imaging experiments. In Diels-Alder reactions with tetrazines, the reaction rate with 2 is similar to that with the parent TCO.…”

Section: Introductionmentioning

confidence: 99%

“…More recently, Dudley, Alabugin and coworkers have shown ( in silico ) that 3-oxocyclooctynes display fast reactivity in cycloadditions with azides, and have attributed their fast reactivity partly to the hyperconjugative effect of the allylic oxygens 37. Tomooka and Woerpel have synthesized trans -oxasilacycloalkenes, and have studied their reactivity in Diels–Alder and azide cycloadditions 38,39. Very recently, Lemke, Kele and coworkers reported the genetic incorporation of dioxo-TCO 2 and demonstrated that the lower lipophilicity of this molecule resulted in improved washout times during imaging experiments.…”

Section: Introductionmentioning

confidence: 99%

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Computationally guided discovery of a reactive, hydrophilic trans-5-oxocene dienophile for bioorthogonal labeling

et al. 2017

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Computationally guided discovery of a reactive, hydrophilic trans-5-oxocene dienophile for bioorthogonal labeling

et al. 2017

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“…In a seminal contribution, Jendrella synthesized 4,6-dioxo-TCO 13 and showed it to be more reactive than transcyclooctene in cycloadditions with cyclopentadiene, 2,3dimethylbutadiene, mesitonitriloxide and diphenylketene. [139] Woerpel [49][50][51][52][53][54][55][56][57] and Tomooka [62] have synthesized trans-oxasilacycloalkenes, and have studied their reactivity in Diels-Alder and azide cycloadditions. Kele, Lemke and coworkers reported the genetic incorporation of dioxo-TCO 14 and demonstrated that the lower lipophilicity of this molecule resulted in improved washout times during imaging experiments.…”

Section: Trans-cyclooctenes In Bioorthogonal Chemistrymentioning

confidence: 99%

“…[148] Because CÀ Si bonds are long, the inclusion of silicon into the cyclic backbone can alleviate olefinic strain and impart stability to trans-cycloalkenes. [52][53][54][55][56][57]62] Woerpel has developed a general method for the preparation of trans-oxasilacycloheptenes-seven membered rings that contain trans-alkenes and siloxy bonds in the backbone (Figure 14), and has described their selective addition, difunctionalization and cycloaddition reactions. [52][53][54][55][56][57] Several studies had shown that metal complexes of transcycloheptene can be isolated.…”

Section: Flow Photochemical Synthesis Of Trans-cycloheptenes and Silamentioning

confidence: 99%

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Flow Photochemical Syntheses of trans‐Cyclooctenes and trans‐Cycloheptenes Driven by Metal Complexation

Pigga

Fox

2019

Israel Journal of Chemistry

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trans-Cyclooctenes and trans-cycloheptenes have long been the subject of physical organic study, but the broader application had been limited by synthetic accessibility. This account describes the development of a general, flow photochemical method for the preparative synthesis of trans-cycloalkene derivatives. Here, photoisomerization takes place in a closed-loop flow reactor where the reaction mixture is continuously cycled through Ag(I) on silicagel. Selective complexation of the trans-isomer by Ag(I) during flow drives an otherwise unfavorable isomeric ratio toward the transisomer. Analogous photoreactions under batch-conditions are low yielding, and flow chemistry is necessary in order to obtain trans-cycloalkenes in preparatively useful yields. The applications of the method to bioorthogonal chemistry and stereospecific transannulation chemistry are described.The unusual reactivity and well-defined chiral structure of trans-cycloalkenes has made them attractive targets for synthesis for nearly 70 years. [1][2][3] For example, trans-cyclooctene possesses planar chirality and displays a high barrier to racemization (E a = 35.6 kcal/mol), [4] and the most stable "crown" conformer has an alternating sequence of equatorial and axial hydrogens that is akin to chair cyclohexane. [5][6] The double bond of trans-cyclooctene is twisted severely in the crown conformation, [7] and as a consequence the HOMO of trans-cyclooctene is relatively high in energy. [8] trans-Cycloheptene also has a rigid structure with a distorted alkene. [7] The double bonds of medium-ring trans-alkenes are twisted. [7] trans-Cycloalkenes display unusual reactivity in HOMOalkene controlled cycloaddition reactions with dienes, [9] 1,3dipoles [8] and ketenes. [10] Strained trans-cycloalkenes also serve as ligands for transition metals. [11][12][13][14][15][16] This reactivity profile has made trans-cycloalkanes interesting targets for applications in synthesis and biology.The broadest applications of trans-cycloalkenes are in the field of bioorthogonal chemistry. The inverse-electron demand Diels-Alder reaction between tetrazines and strained alkenes has a rich history in physical organic and synthetic chemistry (Figure 1). [17][18][19] In 2008, three groups described the bioorthogonal reactions of tetrazines with strained alkenes. [20][21][22] The variant introduced by our group that used trans-cyclooctene is marked by exceptionally rapid kinetics, with rate constants that can exceed 10 6 M À 1 s À 1 in the fastest cases. [23][24] With the advances including the development of fluorogenic tetrazines [25] and reactions in live cells [26] and animals, [27] the tetrazine ligation has become a widely used tool for applications that span chemical biology, biomedical imaging, and materials science. [28][29][30][31][32][33][34][35][36][37] This account describes the development of general, flow photochemical methods for the preparative synthesis of transcycloalkene derivatives and enabled applications in synthesis and bioorthogonal chemistry. Selectiv...

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Construction of Six‐Membered Silacyclic Skeletons via Platinum‐Catalyzed Tandem Hydrosilylation/Cyclization with Dihydrosilanes

Long

Bai

et al. 2018

Adv Synth Catal

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Catalytic silicon‐carbon or silicon‐heteroatom bond‐forming hydrosilylation has become increasingly important in synthetic chemistry, catalysis and organosilicon chemistry. Herein we report a platinum‐catalyzed one‐pot and tandem hydrosilylation/cyclization of OH‐containing alkynes with dihydrosilanes, allowing for facile synthesis of six‐membered organosilicon compounds, including silyloxycycles and cyclic siloxanes in high yields and with good stereoselectivities.magnified image

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[4+2] Cycloadditions of Seven‐Membered‐Ring trans‐Alkenes: Decreasing Reactivity with Increasing Substitution of the Seven‐Membered Ring

Cited by 20 publications

References 52 publications

Computationally guided discovery of a reactive, hydrophilic trans-5-oxocene dienophile for bioorthogonal labeling

Computationally guided discovery of a reactive, hydrophilic trans-5-oxocene dienophile for bioorthogonal labeling

Flow Photochemical Syntheses of trans‐Cyclooctenes and trans‐Cycloheptenes Driven by Metal Complexation

Construction of Six‐Membered Silacyclic Skeletons via Platinum‐Catalyzed Tandem Hydrosilylation/Cyclization with Dihydrosilanes

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