Enantioselective, Lewis Base-Catalyzed Sulfenocyclization of Polyenes

Tao, Zhong‐Lin; Robb, Kevin A.; Zhao, Kuo; Denmark, Scott E.

doi:10.1021/jacs.8b01660

Cited by 115 publications

(79 citation statements)

References 57 publications

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“…The sulfenium ion can be considered as the sulfur analogue of carbenium [30] or nitrenium ions [30][31] and are generally prepared by activation of S-arylthiophthalimides. [12,32] However, we have shown here that no prefunctionalization of the substrates or any template approach were necessary for this cross dehydrogenative CÀS coupling reaction of arenes and thiols, and the sulfenium ions could be generated in situ by oxidation of thiols. Unprecedentedly, we report here the generation of sulfenium ion using hypervalent iodine(III) reagents.…”

Section: Resultsmentioning

confidence: 90%

“…[4] For many years, synthesis of CÀS bonds [5] were usually based on the transition metal catalyzed cross couplings [6] of aryl halides with thiophenols. [11] However, among metal free methods, [12] most of the coupling reactions are reported via prefunctionalization of the substrates. [8] Similarly, Ni, Co, Pd, or Cu metal catalyzed coupling reactions of aryl halides or template assisted synthesis are described in Figure 1a and Figure 1b, respectively.…”

Section: Introductionmentioning

confidence: 99%

“…[9] Aryl sulfenylation [10] and sulfoxidation under photocatalytic condition have also recently been developed but the method contains drawback such as use of thiosulfate salts. [11] However, among metal free methods, [12] most of the coupling reactions are reported via prefunctionalization of the substrates. [13] Therefore, dehydrogenative coupling reactions via non-requirement of prefunctionalized substrates are mostly desirable, for example our present approach is shown in Figure 1c.…”

Section: Introductionmentioning

confidence: 99%

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Iodine(III) Enabled Dehydrogenative Aryl C−S Coupling by in situ Generated Sulfenium Ion

2019

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Due to the normal polarity preferences, arenes form stable complexes with thiols through SÀH···p interaction and direct dehydrogenative aryl CÀS coupling is usually restricted. We report here an umpolung based one pot and direct CÀS coupling approach under metal free and mild condition. Electrophile sulfenium ions were generated in situ from thiols using iodine(III) reagent PhI(OAc) 2 (PIDA) and subsequently used for aromatic electrophilic substitution (EArS) to synthesize diaryl sulfides. Also by using of appropriate amount of PIDA, cascaded synthesis of CÀS and S=O bonds led to aryl sulfinyl arenes in one pot. Covalent self-sorting or competitive experiments further confirmed the involvement of sulfenium ion in the EArS.

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Section: Resultsmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Iodine(III) Enabled Dehydrogenative Aryl C−S Coupling by in situ Generated Sulfenium Ion

2019

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“…are generallyu sed routinely. [36] In ethanol solvent, sulfenium ions were generated in situ using molecular iodine as catalysta nd DMAP-water as ap romoter of the reaction (vide infra). [35] Due to the SÀH···p interaction, hydrogens of thiols prefer to form as table complex with the p-electrons of arenes (Scheme1a).…”

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confidence: 99%

Unsymmetrical Disulfides Synthesis via Sulfenium Ion

Parida

Choudhuri

Mal

2019

Chemistry An Asian Journal

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An umpolunga pproachf or the synthesis of unsymmetrical disulfides via sulfenium ion is reported.I ns itu generated electrophilic sulfeniumi on from electron-rich thiols reacted with second thiols to yield unsymmetrical disulfides. Using an iodine catalysta nd 4-dimethylaminopyridine (DMAP)/water as promoter,t he target syntheses were achieved in one pot under aerobic condition.Organicd isulfides are important functional moieties found in variousm arine natural products, [1] pharmaceuticals, [2] materials [3] and polymers. [4] Disulfides are also known for their odors especially in kitchen items, like in onions and garlics. [5] Pharmaceutically active disulfides are known to have anti-inflammatory, [6] antitumour, [7] antioxidants [8] and antiulcer [9] activities. Chemically,o rgano-disulfides are being used in catalyst, [10] in ligand designing, [11] towards producing fine chemicals andi n functional group protections. [12] In addition, the concept of constitutional dynamic chemistry (CDC) [13] and dynamic combinatorial chemistry (DCC) [14] is documented using the chemistry of disulfides. Due to the reversibility nature of the disulfide bond, formation of many products could be possible when more than one thiol building blocks present in equilibrium. [15] Therefore, it's always challengingt os ynthesize selectively any unsymmetrical disulfides from mixtureo ft hiols in one pot. [16] In Figure 1a,f ew examples of either pharmaceutically important or naturallyo ccurring molecules containing disulfides functionalities are shown. [16b] The known approaches for the synthesis of disulfides are mainly based on using molecular oxygen, [17] transition metals, [18] phosphine-free cationic rhodium(I) complex catalyst, [19] Cu I -phenanthroline catalyst, [20] base catalyzed, [21] non-transition metals, [22] oxidants, [23] sodium perborate, [24] metal organicf rame works (MOFs), [25] microwavea ssisted, [26] electrochemical methods, [27] etc. Recently Dethe and co-workersd eveloped synthesis of unsymmetrical disulfides using fac-Ir(ppy) 3 as photocatalyst and visible light from white LED (Figure 1b). [28] Similarly,u nsymmetrical disulfide synthesis is also reported using O 2 as the oxidant and cobalt(II)phthalocyanine-tetra-sodium sulfonate as the catalyst (Figure 1b). [29] Herein, we reporto ne pot synthesis of unsymmetrical organodisulfides ( Figure 1c)v ia umpolung approach in ethanol sol-

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“…This method also provides access to aw ide variety of enantioenriched carboand heterocycles,i ncluding complex polycyclic natural products. [16] Given our interest in developing ag eneral and enantioselective process for the construction of substituted isochromans (and their tetrahydropyran parents), we envisioned the sulfenium-ion-initiated cascade acetalization in Scheme 1B. In this case,atetrahydropyran ring is generated by the opening of athiiranium ion with asuitably disposed aldehyde oxygen atom, [17] and the resulting oxocarbenium ion is then captured by as econd nucleophile in an intermolecular fashion.…”

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confidence: 99%

Enantio‐ and Diastereoselective, Lewis Base Catalyzed, Cascade Sulfenoacetalization of Alkenyl Aldehydes

Matviitsuk

Denmark

2019

Angewandte Chemie

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Ac atalytic, enantio-, and diastereoselective formation of sulfenyl acetals bearing multiple stereogenic centers is reported. Alkenyl aldehydes undergo ac hiral thiiranium ion initiated cascade starting with intramolecular capture by aformyl group and termination by capture with HFIP solvent. This method provides aone-pot synthesis of dihydropyran and 1,3-disubstituted isochroman acetals in good to excellent yield and with high levels of diastereo-(up to > 99:1 dr) and enantiocontrol (up to 99:1 er).

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Enantioselective, Lewis Base-Catalyzed Sulfenocyclization of Polyenes

Cited by 115 publications

References 57 publications

Iodine(III) Enabled Dehydrogenative Aryl C−S Coupling by in situ Generated Sulfenium Ion

Iodine(III) Enabled Dehydrogenative Aryl C−S Coupling by in situ Generated Sulfenium Ion

Unsymmetrical Disulfides Synthesis via Sulfenium Ion

Enantio‐ and Diastereoselective, Lewis Base Catalyzed, Cascade Sulfenoacetalization of Alkenyl Aldehydes

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