Photoredox‐Mediated Reaction of <i>gem</i>‐Diborylalkenes: Reactivity Toward Diverse 1,1‐Bisborylalkanes

Kumar, N. N. Bhuvan; Eghbarieh, Nadim; Stein, Tamar; Shames, Alexander I.; Masarwa, Ahmad

doi:10.1002/chem.202000603

Cited by 39 publications

(55 citation statements)

References 61 publications

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“…Recently, we reported a photoredox-mediated reaction of gem- diborylalkenes and showed that gem -diborylalkenes 2 have similar electron deficiency as vinylboron 1 ; hence, 2 should serve as a suitable dienophile for this type of cycloaddition reaction. However, key challenges include (1) the steric repulsion introduced by the two groups of the bulky Bpin units in the TS of the cycloaddition reaction; (2) whether the regio- and stereoselectivity of the cycloaddition can be controlled when two unsymmetrical boron groups are placed on the geminated carbon of dienophile 2′ ; and (3) whether the reaction can proceed in a regioselective manner when borylated dienes react with 2 (Figure B) …”

Section: Resultsmentioning

confidence: 99%

“…In recent years, gem -diboryl compounds 2 and 3′ have been widely adopted as coupling partners in synthetic chemistry. 11 , 20 For example, gem -diborylalkenes 2 have served as building blocks for Suzuki–Miyaura cross-coupling, nucleophilic partners, reduction approaches, Michael additions, 21 radical chemistry, 22 and other reactions. 13 , 23 …”

Section: Introductionmentioning

confidence: 99%

“…Among polyboron-containing structural motifs, (unsymmetrical) gem- diboron derivatives ( 2 , 3′ ) are a well-known emerging class with good potential for novel synthetic applications (Figure A). − The special properties and structures of bisnucleophile gem -diboryl compounds 2 and 3′ (termed geminated organodimetallics) , have attracted increasing attention from synthetic chemists, particularly in constructing C–C/C–heteroatom bonds. In recent years, gem -diboryl compounds 2 and 3′ have been widely adopted as coupling partners in synthetic chemistry. , For example, gem -diborylalkenes 2 have served as building blocks for Suzuki–Miyaura cross-coupling, nucleophilic partners, reduction approaches, Michael additions, radical chemistry, and other reactions. , …”

Section: Introductionmentioning

confidence: 99%

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Stereoselective Diels–Alder Reactions of gem-Diborylalkenes: Toward the Synthesis of gem-Diboron-Based Polymers

et al. 2021

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Although gem -diborylalkenes are known to be among the most valuable reagents in modern organic synthesis, providing a rapid access to a wide array of transformations, including the construction of C–C and C-heteroatom bonds, their use as dienophile-reactive groups has been rare. Herein we report the Diels–Alder (DA) reaction of (unsymmetrical) gem -diborylalkenes. These reactions provide a general and efficient method for the stereoselective conversion of gem -diborylalkenes to rapidly access 1,1-bisborylcyclohexenes. Using the same DA reaction manifold with borylated-dienes and gem- diborylalkenes, we also developed a concise, highly regioselective synthesis of 1,1,2-tris- and 1,1,3,4-tetrakis(boronates)cyclohexenes, a family of compounds that currently lack efficient synthetic access. Furthermore, DFT calculations provided insight into the underlying factors that control the chemo-, regio-, and stereoselectivity of these DA reactions. This method also provides stereodivergent syntheses of gem- diborylnorbornenes. The utility of the gem- diborylnorbornene building blocks was demonstrated by ring-opening metathesis polymerization (ROMP), providing a highly modular approach to the first synthesis of the gem- diboron-based polymers. Additionally, these polymers have been successfully submitted to postpolymerization modification reactions. Given its simplicity and versatility, we believe that this novel DA and ROMP approach holds great promise for organoboron synthesis as well as organoboron-based polymers and that it will result in more novel transformations in both academic and industrial research.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Stereoselective Diels–Alder Reactions of gem-Diborylalkenes: Toward the Synthesis of gem-Diboron-Based Polymers

et al. 2021

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“…Although the [4+2] cycloaddition reactions of vinylboranates, 26 e.g., 1, are well documented in the literature (Figure 2A), [27][28][29][30] to the best of our knowledge, the use of gem-diboryllkenes (2) in these types of reactions is rare, despite the potential to provide new and efficient strategies to efficiently construct complex molecules (Figure 2B). 28,30 Recently, we reported a photoredox-mediated reaction of gemdiborylalkenes 31 and showed that gemdiboryalkenes (2) are more electron deficient compared to vinyl-boron 1; 31 hence, 2 should serve as a suitable dienophile for this type of cycloaddition reaction. However, key challenges include: (1) the steric repulsion introduced by the two groups of the bulky Bpin units in the TS of the cycloaddition reaction 32 (2) whether the regio-and stereoselectivity of the cycloaddition can be controlled when two unsymmetrical boron groups are placed on the geminated carbon of dienophile 2' 13 (3) whether the reaction can proceed in a regioselective manner when borylated dienes react with 2 (Figure 2B)?…”

Section: Resultsmentioning

confidence: 99%

Stereoselective Diels-Alder Reactions of gem-Diborylalkenes: Toward the Synthesis of gem-Diboron-Based Polymers via ROMP

Eghbarieh¹,

Hanania²,

Zamir³

et al. 2021

Preprint

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Although gem-diborylalkenes are known to be among the most valuable reagents in modern organic synthesis, providing a rapid access to a wide array of transformations, including the construction of C−C and C‐heteroatom bonds, their use as dienophile-reactive groups has been rare. Herein we report the Diels-Alder (DA) reaction of (unsymmetrical) gem-diborylalkenes. These reactions provide a general and efficient method for the stereoselective conversion of gem-diborylalkenes to rapidly access 1,1-bisborylcyclohexenes. Using the same DA reaction manifold with borylated-dienes and gem-diborylalkenes, we also developed a concise, highly regioselective synthesis of 1,1,2-tris- and 1,1,3,4-tetrakis(boronates)cyclohexenes, a family of compounds that currently lack efficient synthetic access. Furthermore, DFT calculations provided insight into the underlying factors that control the chemo-, regio, and stereoselectivity of these DA reactions. This method also provides stereodivergent syntheses of gem-diboryl-norbornenes. The utility of the gem-diboryl-norbornene building blocks was demonstrated by ring-opening metathesis polymerization (ROMP), providing a highly modular approach to the first synthesis of the gem-diboron-based polymers. Given its simplicity and versatility, we believe that this novel DA and ROMP approach holds great promise for organoboron synthesis as well as organoboron-based polymers and that it will result in more novel transformations in both academic and industrial research.<br>

show abstract

Section: Resultsmentioning

confidence: 99%

Stereoselective Diels-Alder Reactions of gem-Diborylalkenes: Toward the Synthesis of gem-Diboron-Based Polymers via ROMP

Eghbarieh¹,

Hanania²,

Zamir³

et al. 2021

Preprint

Self Cite

View full text Add to dashboard Cite

Although gem-diborylalkenes are known to be among the most valuable reagents in modern organic synthesis, providing a rapid access to a wide array of transformations, including the construction of C−C and C‐heteroatom bonds, their use as dienophile-reactive groups has been rare. Herein we report the Diels-Alder (DA) reaction of (unsymmetrical) gem-diborylalkenes. These reactions provide a general and efficient method for the stereoselective conversion of gem-diborylalkenes to rapidly access 1,1-bisborylcyclohexenes. Using the same DA reaction manifold with borylated-dienes and gem-diborylalkenes, we also developed a concise, highly regioselective synthesis of 1,1,2-tris- and 1,1,3,4-tetrakis(boronates)cyclohexenes, a family of compounds that currently lack efficient synthetic access. Furthermore, DFT calculations provided insight into the underlying factors that control the chemo-, regio, and stereoselectivity of these DA reactions. This method also provides stereodivergent syntheses of gem-diboryl-norbornenes. The utility of the gem-diboryl-norbornene building blocks was demonstrated by ring-opening metathesis polymerization (ROMP), providing a highly modular approach to the first synthesis of the gem-diboron-based polymers. Given its simplicity and versatility, we believe that this novel DA and ROMP approach holds great promise for organoboron synthesis as well as organoboron-based polymers and that it will result in more novel transformations in both academic and industrial research.<br>

show abstract

Photoredox‐Mediated Reaction of gem‐Diborylalkenes: Reactivity Toward Diverse 1,1‐Bisborylalkanes

Abstract: Scheme2.Scope of the synthesis of gem-diborylalkanes, the proposed mechanism and ad euterium-labelling study.

Cited by 39 publications

References 61 publications

Stereoselective Diels–Alder Reactions of gem-Diborylalkenes: Toward the Synthesis of gem-Diboron-Based Polymers

Stereoselective Diels–Alder Reactions of gem-Diborylalkenes: Toward the Synthesis of gem-Diboron-Based Polymers

Stereoselective Diels-Alder Reactions of gem-Diborylalkenes: Toward the Synthesis of gem-Diboron-Based Polymers via ROMP

Stereoselective Diels-Alder Reactions of gem-Diborylalkenes: Toward the Synthesis of gem-Diboron-Based Polymers via ROMP

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