Pd-Catalyzed Conversion of Alkynyl-λ<sup>3</sup>-iodanes to Alkenyl-λ<sup>3</sup>-iodanes via Stereoselective 1,2-Iodine(III) Shift/1,1-Hydrocarboxylation

Wu, Junliang; Deng, Xiaozhou; Hirao, Hajime; Yoshikai, Naohiko

doi:10.1021/jacs.6b06247

Cited by 70 publications

(50 citation statements)

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“…[13] Ochiai reported at ransition-metalfree anti-hydrochlorinationo fa lkynyl(phenyl)iodonium tetrafluoroborate by using LiCl/HOAc or HCl/MeOH, whereas the scope of the reaction was demonstrated for only ah andful of iodoniums alts. [14,15] By contrastt ot hese precedents,t he present anti-hydrochlorination, found during our study on the Pd-catalyzed 1,1-hydrocarboxylation, [6] was achieved under extremely simple conditions. Thus, the reaction between Ph-EBX 1a and pyridine hydrochloride (Py·HCl, 2equiv) proceeded smoothly in EtOAc at 50 8Cu nder air,a ffording the VBX product 2a in quantitative yield exclusively as a cis isomer (Table 1, entry 1).…”

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confidence: 73%

“…We disclosed palladium-catalyzed 1,1-hydrocarboxylation of various substituted EBXs by a1 ,2-iodine(III) shift, affordingV BXs bearing an enol carboxylate moiety (Scheme 1a). [6,7] Miyake reported anti-addition of phenols to aryl-EBXs under visible-light irradiation (Scheme 1b), in which the primary VBX product readily transforms into iodovinylether. [8] More recently,W aser has found simple conditions that allow fort he anti-addition of sulfonamides and phenolst oa lkyl-EBXs with retention of the BX moiety in the products.…”

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confidence: 99%

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Stereocontrolled Synthesis of Halovinylbenziodoxoles by Hydro‐ and Iodochlorination of Ethynylbenziodoxoles

Deng

Yoshikai

2019

Chemistry A European J

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We report herein the synthesis of highly substituted and stereochemically well-definedv inylbenziodoxole (VBX) derivatives through hydrochlorination and iodochlorination of ethynylbenziodoxoles.T he hydrochlorination is achieved using pyridine hydrochloridea sa nH Cl source in an anti-fashion under mild, open-air conditions to afford a2 -chlorinatedV BX product, which serves as a useful building block for the stereoselective synthesis of trisubstituted alkenes.M eanwhile, iodochlorination with iodine monochloride proceeds in an unusual syn-pathway, stereoselectively affording at etrasubstituted VBX derivative.Hypervalent iodine compounds bearing benziodoxol(on)e (BX) backboneh ave emerged as versatile electrophilic group-transfer agentsi no rganic synthesis, as the cyclic BX moiety endows the reagents with well-balanced stabilitya nd reactivity suited under broad range of reactionc onditions. [1] Amongv arious BX-based group transferr eagents, ethynyl-BXs( EBXs) have found numerous applicationsi nC -alkynyl and heteroatom-alkynyl bond formationss ince the pioneering work of Waser. [1a-d, 2-4] Meanwhile,t his class of compounds has also found unique synthetic applications beyonds imple alkynyl group transfer,i nw hich the BX group does not act as am ere leaving group but as an integralp art of the product. [5] In this context,E BXs have been found to serve as ap recursor to functionalized vinyl-BXs (VBXs), whichw ould serve as novel alkenyl group-transfer agents that are otherwise difficultt oa ccess. We disclosed palladium-catalyzed 1,1-hydrocarboxylation of various substituted EBXs by a1 ,2-iodine(III) shift, affordingV BXs bearing an enol carboxylate moiety (Scheme 1a). [6,7] Miyake reported anti-addition of phenols to aryl-EBXs under visible-light irradiation (Scheme 1b), in which the primary VBX product readily transforms into iodovinylether. [8] More recently,W aser has found simple conditions that allow fort he anti-addition of sulfonamides and phenolst oa lkyl-EBXs with retention of the BX moiety in the products. [9,10] As highly functionalized VBX compounds hold promise as versatile synthetic building blocks for stereodefined alkenes, [11] furtherd evelopment of EBX-to-VBX transformations is highly desirable.Herein, we report on stereoselective hydrochlorination and iodochlorination reactions of EBX, affording stereochemically well-defined halogenated VBX compounds (Scheme1c). The formerr eactionw as achievedu sing pyridineh ydrochloride in an exclusive anti-fashion, affording au seful buildingb lock for the stereoselective synthesiso fm ultisubstituted alkenes. The latter reactionu sing iodine monochloride features an unusual syn-addition pathway,a ffording an exotic tetrasubstituted VBX product.Hydrochlorination of haloalkynes offers as traightforward approacht oward synthetically useful 1,2-chlorohaloalkenes. Zhu and Xu independently achieved anti-hydrochlorinationo fh aloalkynes with LiCl/HOAc using palladium and gold catalysts, respectively, [12] which likely involved anti-chlorometalation of the C...

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Stereocontrolled Synthesis of Halovinylbenziodoxoles by Hydro‐ and Iodochlorination of Ethynylbenziodoxoles

Deng

Yoshikai

2019

Chemistry A European J

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“…81 The reactions, which were promoted by the [Pd(OAc)(2-methylallyl)]2/1,5-cyclooctadiene system under very mild conditions (r.t.), led to the selective formation of the alkenylbenziodoxoles 17. Density functional theory (DFT) calculations indicated that this unprecedented rearrangement/addition process involves the formation of a Pd-vinylidene intermediate VI, via 1,2-shift of the iodine(III) fragment on the initially formed π-alkyne species V. Then, a formal 1,1-hydroxycarboxylation takes place by nucleophilic addition of the carboxylate anion on the α-carbon of the vinylidene intermediate VI, and subsequent protodemetalation of the resulting alkenyl-palladate VII.…”

Section: Methodsmentioning

confidence: 99%

The intermolecular hydro-oxycarbonylation of internal alkynes: current state of the art

González-Liste¹,

Francos²,

García‐Garrido³

et al. 2017

Arkivoc

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The intermolecular addition of carboxylic acids to alkynes is one of the most straightforward and atomeconomical methods currently available for the preparation of synthetically useful enol esters. However, the vast majority of works have focused on the use of terminal alkynes, substrates much more reactive than their corresponding internal counterparts. In fact, efficient and general protocols for hydro-oxycarbonylation of internal alkynes have only seen the light in recent years. In the present review article an overview of the progress made in the field is given. Catalytic reactions promoted by ruthenium, palladium, silver and gold complexes/salts, along with some specific metal-free protocols, are covered.

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“…Recently, Hirao et al have reported a Pd(II) catalyzed 1,1‐hydrocarboxylation of alkynyl benziodoxole 1 as shown in Scheme (a) . The palladium pre‐catalyst and the ligand combination play a crucial role in the reaction.…”

Section: Alkynylationmentioning

confidence: 99%

Hypercoordinate iodine(III) promoted reactions and catalysis: an update on current mechanistic understanding

Sreenithya

Surya

Sunoj

2017

WIREs Comput Mol Sci

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Mild and environment friendly hypercoordinate iodine compounds exhibit promising reactivities resembling that of transition metal catalysts. Hypercoordinate iodine reagents or catalysts are increasingly been employed in contemporary organic synthesis. However, mechanistic insights on such reactions continue to remain rather limited. Recent advances in the mechanistic understanding on a selected set of reactions involving hypercoordinate iodine form the main theme of this review. An overview of bonding, reactivity, and mechanistic insights on iodine(III) reactions such as α-functionalization of carbonyl compounds, alkynylation, amination, C H functionalization, phenol dearomatization, and trifluoromethylation have been described. In keeping with the current practices in mechanistic studies, we have maintained an interdisciplinary flavor in this compilation by providing a balanced view of computational and experimental understanding on the burgeoning domain of hypercoordinate iodine mediated reactions and catalysis. FIGURE 1 | Molecular orbital (MO) diagram for three-center-fourelectron (3c-4e) bond in hypercoordinate iodine compound RIL 2 . SCHEME 1 (a) General representation of α-tosyloxylation ketone catalyzed by Koser's reagent. (b) General mechanism for the α-tosyloxylation ketone. (c) Commonly employed iodoarenes in α-tosyloxylation. Overview wires.wiley.com/compmolsci SCHEME 2 (a) Effect of different substituents on the catalytic activity of iodoaryl in α-tosyloxylation. (b) Effect of different substituents on dihedral angle θ(C1-C2-I3-O4). (c) Formation of iodono intermediate 4 and the related ΔG rxn . WIREs Computational Molecular Science Hypercoordinate iodine(III) promoted reactions and catalysis Volume 7,

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Pd-Catalyzed Conversion of Alkynyl-λ³-iodanes to Alkenyl-λ³-iodanes via Stereoselective 1,2-Iodine(III) Shift/1,1-Hydrocarboxylation

Cited by 70 publications

References 32 publications

Stereocontrolled Synthesis of Halovinylbenziodoxoles by Hydro‐ and Iodochlorination of Ethynylbenziodoxoles

Stereocontrolled Synthesis of Halovinylbenziodoxoles by Hydro‐ and Iodochlorination of Ethynylbenziodoxoles

The intermolecular hydro-oxycarbonylation of internal alkynes: current state of the art

Hypercoordinate iodine(III) promoted reactions and catalysis: an update on current mechanistic understanding

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Pd-Catalyzed Conversion of Alkynyl-λ3-iodanes to Alkenyl-λ3-iodanes via Stereoselective 1,2-Iodine(III) Shift/1,1-Hydrocarboxylation

Cited by 70 publications

References 32 publications

Stereocontrolled Synthesis of Halovinylbenziodoxoles by Hydro‐ and Iodochlorination of Ethynylbenziodoxoles

Stereocontrolled Synthesis of Halovinylbenziodoxoles by Hydro‐ and Iodochlorination of Ethynylbenziodoxoles

The intermolecular hydro-oxycarbonylation of internal alkynes: current state of the art

Hypercoordinate iodine(III) promoted reactions and catalysis: an update on current mechanistic understanding

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Pd-Catalyzed Conversion of Alkynyl-λ³-iodanes to Alkenyl-λ³-iodanes via Stereoselective 1,2-Iodine(III) Shift/1,1-Hydrocarboxylation