Rhodium‐Catalyzed Allylic Substitution Reactions with Indium(III) Organometallics

Riveiros, Ricardo; Tato, Rubén; Sestelo, José Pérez; Sarandeses, Luis A.

doi:10.1002/ejoc.201200104

Cited by 16 publications

(4 citation statements)

References 66 publications

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Section: Triorganoindium Reagentmentioning

confidence: 63%

“…A very recent contribution from the same group demonstrated that such allylic substitution can be catalyzed by rhodium catalyst with a lower organoindium loading (0.5 equiv) (Scheme 561). 774 Like the aforementioned palladiumcatalyzed reaction, the present protocol also worked well to give α-substituted products in good yields with excellent regioselectivity. Secondary allylic chloride can be used as well by using 0.7 equiv of triarylindium reagent, although a partial isomerization of the C−C double bond was observed that might be due to the formation of a π-allylrhodium intermediate in the reaction.…”

Section: Application In Organic Synthesismentioning

confidence: 66%

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Organoindium Reagents: The Preparation and Application in Organic Synthesis

et al. 2012

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allylation performed in aqueous media, an efficient synthesis of highly functionalized lactones was realized in good yields (64− 77%, Scheme 29). 238 However, the chirality installed during the first step almost had no influence on the second step, thus resulting in poor diastereoselectivity in the subsequent allylation reaction (1:1−2:1 dr).In situ formation of aldehyde from the oxidation of alcohol followed by one-pot indium-mediated allylation also provides an alternative method for the synthesis of homoallylic alcohol. Recently, Yadav and co-workers developed such a one-pot sequence by using chloramines-T (sodium salt of Nchlorotosylamide) as oxidant in the presence of a catalytic amount of FeCl 3 in CH 2 Cl 2 , giving rise to homoallylic alcohols in good to excellent yields (Scheme 30). 239 It is noteworthy that the generated byproduct of TsNH 2 (from the reduction of chloramines-T) may react with the in situ-formed aldehydes to give intermediates of N-tosylimines in the presence of 4 Å molecular sieve under refluxing; the thus-formed N-tosylimines subsequently underwent one-pot indium-mediated allylation to produce homoallylic amines in 60−80% yields. Later, a similar one-pot, two-step sequence for the synthesis of homoallylic alcohols via a galactose oxidase-mediated chemo-enzymatic oxidation of benzyl and cinnamyl alcohols to the corresponding Scheme 23 Scheme 24 Scheme 25 Scheme 26 Scheme 27 Scheme 28 Scheme 29 Scheme 30 Chemical Reviews Review dx.

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Section: Triorganoindium Reagentmentioning

confidence: 63%

Section: Application In Organic Synthesismentioning

confidence: 66%

Organoindium Reagents: The Preparation and Application in Organic Synthesis

et al. 2012

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“…Since these initial reports, relatively little progress has been made toward using hard nucleophiles in the rhodium-catalyzed allylic substitution reaction . Hence, there is significant room for further development in this area, particularly with regard to the use of unstabilized sp 3 -hybridized nucleophiles …”

Section: Regio- and Stereospecific Rhodium-catalyzed Allylic Substitu...mentioning

confidence: 99%

Asymmetric Rhodium-Catalyzed Allylic Substitution Reactions: Discovery, Development and Applications to Target-Directed Synthesis

2018

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The transition metal-catalyzed allylic substitution reaction is a particularly versatile method for the construction of carbon-carbon and carbon-heteroatom bonds. In this regard, the rhodium-catalyzed variant has emerged as a powerful method for the regioselective and stereospecific allylic substitution of chiral nonracemic secondary and tertiary allylic carbonates with a variety of carbon- and heteroatom-based nucleophiles. In addition, recent developments have made the analogous enantioselective process possible using prochiral nucleophiles with achiral allylic electrophiles, which represents a significant advance in this area. In this Perspective, the discovery, development and applications of these conceptually orthogonal strategies to target-directed synthesis are discussed, with a particular emphasis given to those methods developed in our laboratory.

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“…In this reaction, triorganoindium reagents (R 3 In) can efficiently couple with a variety of organic electrophiles under palladium catalysis with high atom economy [ 5 , 6 , 7 , 8 ]. The process can be extended to other organoindium reagents [ 9 , 10 , 11 , 12 , 13 ] and transition metals in catalysis [ 14 , 15 , 16 , 17 ].…”

Section: Introductionmentioning

confidence: 99%

Triorganoindium Reagents in Rh-Catalyzed C–H Activation/C–C Cross-Coupling Reactions of 2-Arylpyridines

et al. 2018

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The activation of C–H bonds through catalytic reactions using transition metals is an important challenge in organic chemistry in which the intermediates are related to those produced in the classical cross-coupling reactions. As part of our research program devoted to the development of metal-catalyzed reactions using indium organometallics, a protocol for the C–H activation and C–C coupling of 2-arylpyridines with triorganoindium reagents under Rh(I) catalysis is reported. Under the optimized conditions, we found that Me3In and Ar3In reagents reacted with 2-arylpyridines and related compounds in the presence of Rh(PPh3)3Cl, in PhCl/THF (9:1), at 120 °C for 48 h, to afford the ortho-coupling products in moderate to good yields. The nitrogen atom in the pyridine ring acts as a directing group to assist the functionalization at the ortho position of the aryl group forming a new C–C bond at this position.

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Rhodium‐Catalyzed Allylic Substitution Reactions with Indium(III) Organometallics

Cited by 16 publications

References 66 publications

Organoindium Reagents: The Preparation and Application in Organic Synthesis

Organoindium Reagents: The Preparation and Application in Organic Synthesis

Asymmetric Rhodium-Catalyzed Allylic Substitution Reactions: Discovery, Development and Applications to Target-Directed Synthesis

Triorganoindium Reagents in Rh-Catalyzed C–H Activation/C–C Cross-Coupling Reactions of 2-Arylpyridines

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