Catalytic S<sub>N</sub>2′‐ and Enantioselective Allylic Substitution with a Diborylmethane Reagent and Application in Synthesis

Metal‐catalyzed asymmetric allylic substitution (AAS) reaction is one of the most synthetically useful reactions catalyzed by metal complexes for the formation of carbon‐carbon and carbon‐heteroatom bonds. It comprises the substitution of allylic substrates with a wide range of nucleophiles or SN2′‐type allylic substitution, which results in the formation of the above‐mentioned bonds with high levels of enantioselective induction. AAS reaction tolerates a broad range of functional groups, thus has been successfully applied in the asymmetric synthesis of a wide range of optically pure compounds. This reaction has been extensively used in the total synthesis of several complex molecules, especially natural products. In this review, we try to highlight the applications of metal (Pd, Ir, Mo, or Cu)‐catalyzed AAS reaction in the total synthesis of the biologically active natural products, as a key step, updating the subject from 2003 till date.

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“…The latter wan then transformed into the expected rhopaloic acid A ( 311 ) in several steps (Scheme 62). [233] …”

Section: Copper‐catalyzed Aas Reactionsmentioning

confidence: 99%

Applications of Transition‐Metal‐Catalyzed Asymmetric Allylic Substitution in Total Synthesis of Natural Products: An Update

Mohammadkhani

Heravi

2020

The Chemical Record

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“…Transition metals catalyzed synthesis of monoboration (e.g., Rh 23 , Fe 24 – 27 , Co 28 , 29 , Ir 30 , Ru 31 ), 1,2-diboration (e.g., Rh 32 , 33 , Pt 34 – 36 , Cu 37 , Ni 38 , Pd 39 and metal-free 40 , 41 ) and 1,1,1-triboration 10 of alkenes ( a ). Construction of chiral molecules utilizing racemic or nonracemic 1,1-diborylalkanes 11 – 15 , 42 , 43 ( b ). Conversion C–B bonds to C–C bonds to afford complex molecules ( c ).…”

Section: Introductionmentioning

confidence: 99%

“…As an important class of organoboron compounds, it is undeniable that the 1,1-diborylalkanes show significant applications in organic synthesis. They can either be manipulated in enantioselective catalytic fashion 11 – 15 (Fig. 1b ) and or they can provide powerful synthetic module for concise synthesis of complex molecules through multiple C–C bond formation 16 – 22 (Fig.…”

Section: Introductionmentioning

confidence: 99%

Nickel-catalyzed synthesis of 1,1-diborylalkanes from terminal alkenes

et al. 2017

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Organoboron compounds play an irreplaceable role in synthetic chemistry and the related transformations based on the unique reactivity of C–B bond are potentially the most efficient methods for the synthesis of organic molecules. The synthetic importance of multiboron compounds in C–C bond formation and function transformation reactions is growing and the related borations of activated or nonactivated alkenes have been developed recently. However, introducing directly two boron moieties into the terminal sites of alkenes giving 1,1-diborylalkanes in a catalytic fashion has not been explored yet. Here we describe a synthetic strategy of 1,1-diborylalkanes via a Ni-catalyzed 1,1-diboration of readily available terminal alkenes. This methodology shows high level of chemoselectivity and regioselectivity and can be used to convert a large variety of terminal alkenes, such as vinylarenes, aliphatic alkenes and lower alkenes, to 1,1-diborylalkanes.

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Synthesis and Reactivity of 1,1‐Diborylalkanes towards C–C Bond Formation and Related Mechanisms

2018

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Abstractgem‐Diborylalkanes have emerged as efficient reagents for synthesizing organoboron compounds through selective C−C bond‐forming reactions. Activation of the 1,1‐diborylalkanes generates carbanions with enhanced stability that are able to react with a series of electrophiles, carbonyl compounds, imines and epoxides to promote formation of a new C−C bond. These new sets of reactions have become general for a wide range of substrates and they can be understood by alternative mechanisms that justify the potential use of these reagents. The formation of C–C(B) bonds can be achieved with chemo‐, diastereo‐ and enantioselectivity, because the nucleophilc α‐boryl or α‐diboryl carbanions attack in a stereoselective manner, by means of the catalyst involved. The synthesis of gem‐diborylalkanes has also been promoted by innovative methods and facilitates access to multiborylated reagents with different substituents and properties.magnified image

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Catalytic S_N2′‐ and Enantioselective Allylic Substitution with a Diborylmethane Reagent and Application in Synthesis

Cited by 38 publications

References 61 publications

Applications of Transition‐Metal‐Catalyzed Asymmetric Allylic Substitution in Total Synthesis of Natural Products: An Update

Applications of Transition‐Metal‐Catalyzed Asymmetric Allylic Substitution in Total Synthesis of Natural Products: An Update

Nickel-catalyzed synthesis of 1,1-diborylalkanes from terminal alkenes

Synthesis and Reactivity of 1,1‐Diborylalkanes towards C–C Bond Formation and Related Mechanisms

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Catalytic SN2′‐ and Enantioselective Allylic Substitution with a Diborylmethane Reagent and Application in Synthesis

Cited by 38 publications

References 61 publications

Applications of Transition‐Metal‐Catalyzed Asymmetric Allylic Substitution in Total Synthesis of Natural Products: An Update

Applications of Transition‐Metal‐Catalyzed Asymmetric Allylic Substitution in Total Synthesis of Natural Products: An Update

Nickel-catalyzed synthesis of 1,1-diborylalkanes from terminal alkenes

Synthesis and Reactivity of 1,1‐Diborylalkanes towards C–C Bond Formation and Related Mechanisms

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Catalytic S_N2′‐ and Enantioselective Allylic Substitution with a Diborylmethane Reagent and Application in Synthesis