Regio- and Stereoselective Allylindation of Alkynes Using InBr3 and Allylic Silanes: Synthesis, Characterization, and Application of 1,4-Dienylindiums toward Skipped Dienes

Nishimoto, Yoshihiro; Yi, Junyi; Takata, T.; Baba, Akio; Yasuda, Makoto

doi:10.3390/molecules23081884

Cited by 9 publications

(1 citation statement)

References 46 publications

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“…They also serve as versatile building blocks in chemical synthesis, with applications in the total synthesis of complex natural products. Consequently, several strategies have been developed for the synthesis of skipped dienes, including allylmetalation of alkynes, allylic vinylations, and cross-coupling reactions . Despite their efficiency, strategies to access structurally diverse skipped dienes in high regioselective and stereoselective fashion remain a significant challenge in organic chemistry.…”

Section: Introductionmentioning

confidence: 99%

Rhodium(II)-Catalyzed Strain-Enabled Stereoselective Synthesis of Skipped Dienes

Kadam,

Singha,

Rawat

et al. 2024

ACS Catal.

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Skipped dienes are not only present in fatty acid primary metabolites and natural products but also serve as reactive intermediates in diverse chemical synthesis. Despite this, the regioselective and stereoselective synthesis of skipped dienes remains a challenging goal. Strain release in organic molecules is a powerful tool for creating chemical complexity under mild conditions. The reactivity of strained bicyclo[1.1.0]butane (BCB) systems is mainly dominated by transformations relying on their innate electrophilic reactivity. Herein, we report a rare example of the carbene-type reactivity of the BCB system based on rhodium−carbene chemistry, which enables the highly stereoselective synthesis of skipped dienes through strain release. The reaction is compatible with a diverse range of functional groups on both diazo compounds and BCBs and could be applied successfully to complex structures, providing highly valuable and functionalizable skipped dienes. The functional groups introduced during the reaction served as synthetic handles for downstream manipulations. The high stereoselectivity observed has been rationalized based on DFT calculations, which suggests that the reaction is likely proceeding via a concerted mechanism, and noncovalent interactions between the metallocarbene and BCB mainly control the observed exclusive selectivity.

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Section: Introductionmentioning

confidence: 99%

Rhodium(II)-Catalyzed Strain-Enabled Stereoselective Synthesis of Skipped Dienes

Kadam,

Singha,

Rawat

et al. 2024

ACS Catal.

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Carbometalation and Heterometalation of Carbon‐Carbon Multiple‐Bonds Using Group‐13 Heavy Metals: Carbogallation, Carboindation, Heterogallation, and Heteroindation

Nishimoto

Yasuda

2020

Chemistry An Asian Journal

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Organogallium and ‐indium compounds are useful reagents in organic synthesis because of their moderate stability, efficient reactivity and high chemoselectivity. Carbogallation and ‐indation of a carbon‐carbon multiple bond achieves the simultaneous formation of carbon‐carbon and carbon‐metal bonds. Heterogallation and ‐indation construct carbon‐heteroatom and carbon‐metal bonds. Therefore, these reaction systems represent a significant synthetic method for organogalliums and ‐indiums. Many chemists have attempted to apply various types of unsaturated compounds such as alkynes, alkenes, and allenes to these reaction systems. This minireview provides an overview of carboindation and ‐gallation as well as heteroindation and ‐gallation.

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Synthesis of (Z)‐β‐(Carbonylamino)alkenylindium through Regioselective anti‐Carboindation of Ynamides and Its Transformation to Multisubstituted Enamides

Kang

Sakamoto

Nishimoto

et al. 2020

Chemistry A European J

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The regioselective anti-carboindation of ynamides by usingI nBr 3 and silylated nucleophilesw as developed to synthesize (Z)-b-(carbonylamino)alkenylindiums. The X-ray crystallographic analysis of an alkenylindium suggested that the reaction proceeded in an anti-addition fashion.I nc ontrastt or eported syn-carbometalationso f ynamides by using organometallics, ac ooperation of InBr 3 and silylated nucleophiles to ynamides achieveda nantiaddition, whichw as supportedb yD FT calculations. The scope of substrates included variousy namides and silylated nucleophiles, such as silyl ketenea cetals and silyl ketene imines. The transformation of synthesized alkenylindiumsb yi odination,r adicalc oupling, and Pd-catalyzed cross-couplings uccessfully afforded trisubstituted enamines with high regio-and stereoselectivities.Enamides are versatile buildingb locks for valuable nitrogencontaining compounds. [1] Ac ombinationo fc arbometalations of ynamides and transformations of the formed metalated enamides is one of the most reliable synthetic methods for multisubstituted enamides. [2] In this strategy,e stablishmento fr egioand stereoselective carbometalation is necessary for selectively synthesizing ad esired enamide among possiblei somers. Syncarbometalation of ynamides of organometallic compounds has been widely studied (Scheme1a). For example, a-(carbonylamino)alkenylmetals are obtained through the syn-addition of organocoppers, -zincs,a nd -lithiums to ynamides. [3,4] In contrast, b-(carbonylamino)alkenylmetalsa re obtained by syn-carbopalladation of ynamides by using organopalladiums. [5] How-ever, anti-carbometalation of ynamides remains underdeveloped,a lthough the intramolecular carbometalations of ynamidesh ave been reported (Scheme 1b). [6] We recently reported intermolecular anti-carbometalations of carbon-carbon triple bonds by using silylatedn ucleophiles and metal salts, such as InBr 3 ,G aBr 3 ,A lBr 3 ,B iBr 3 ,a nd ZnBr 2 . [7] Therefore, we assumedo ur strategy could achieve anti-carbometalation of ynamides. Here, we report the anti-carbometalation of ynamides by using InBr 3 and silyl ketene acetals to synthesize (Z)-b-(carbonylamino)alkenylindiums(Scheme 1c).First, we surveyed metal halides fort he carbometalation of N-ethynylpyrrolidone (1a)b yu sing the silyl ketene acetal 2a (Table 1). The reactiono fy namide 1a by using InBr 3 and 2a followed by the addition of MeOH exclusively gave the product 3aa in 96 %y ield, where the carbon-carbon bond was formed at the carbon atom adjacent to the nitrogen atom (Table 1, entry 1). This results howed that enamide 3aa was produced by the protonationo fb-(carbonylamino)alkenylindium (detailsa re described below). Notably,r egioisomers obtainedf rom a-(carbonylamino)alkenylindiumsw ere not found despite the existenceo fa na mide moiety,w hich often serves Scheme1.Carbometalation of ynamides. Entry YnamideProduct [b] Entry YnamideP roduct [b] 1 4 2 5 3 6[a] InBr 3 (0.5 mmol), 1 (0.5 mmol), 2a (1.5 mmol), CH 2 Cl 2 (1 mL), I 2 (1.5 mmol), and DMF (1.5 mL).[b] Y...

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Regio- and Stereoselective Allylindation of Alkynes Using InBr3 and Allylic Silanes: Synthesis, Characterization, and Application of 1,4-Dienylindiums toward Skipped Dienes

Cited by 9 publications

References 46 publications

Rhodium(II)-Catalyzed Strain-Enabled Stereoselective Synthesis of Skipped Dienes

Rhodium(II)-Catalyzed Strain-Enabled Stereoselective Synthesis of Skipped Dienes

Carbometalation and Heterometalation of Carbon‐Carbon Multiple‐Bonds Using Group‐13 Heavy Metals: Carbogallation, Carboindation, Heterogallation, and Heteroindation

Synthesis of (Z)‐β‐(Carbonylamino)alkenylindium through Regioselective anti‐Carboindation of Ynamides and Its Transformation to Multisubstituted Enamides

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