Generating Skeletal Diversity and Complexity from Boron‐Substituted 1,3‐Dienes and Enophiles

François, Benjamin; Eberlin, Ludovic; Berrée, Fabienne; Whiting, Andrew; Carboni, Bertrand

doi:10.1002/ejoc.202000330

Cited by 6 publications

(9 citation statements)

References 97 publications

(40 reference statements)

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“…Remarkably, the reaction of 2 with 3,4-diboryl diene 3l can create the exceptional 1,1,3,4-tetraborylcyclohexene skeleton 4l ( Figure 3 D). Moreover, we examined the DA reaction of 1-boron-diene 34 , 43 E -3k with gem- diborylalkene 2 , and surprisingly, the reaction generated the rare 1,1,2-triboryl cyclic adduct 4k as the exclusive isomer with complete stereospecificity ( Figure 3 E). 12 , 43 , 44 We have obtained unambiguous support for the structures of 4k using X-ray crystallographic analysis (see CYLviews in Figure 3 E).…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, we examined the DA reaction of 1-boron-diene 34 , 43 E -3k with gem- diborylalkene 2 , and surprisingly, the reaction generated the rare 1,1,2-triboryl cyclic adduct 4k as the exclusive isomer with complete stereospecificity ( Figure 3 E). 12 , 43 , 44 We have obtained unambiguous support for the structures of 4k using X-ray crystallographic analysis (see CYLviews in Figure 3 E). DFT calculations indicate that the TS of the 1,1,2-triboryl constitutional isomer is favored by 3 kcal/mol over the TS of the 1,1,3-triboryl isomer ( 1,1,2-triBpin-TS vs 1,1,3-triBpin-TS ; Figure 3 F).…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, the reaction of 2′ with 3,4-diboryl diene 3l yielded 1,1,3,4-tetraborylcyclohexene adduct 5l ( Figure 5 D). Additionally, the DA reaction of 1-boron-diene 34 , 43 ( E -3k ) with gem- diborylalkene 2′ generated regioselectively the separable diastereomers of the 1,1,2-triboryl cyclic adduct with complete stereospecificity ( 5k , 5k′ ; Figure 5 E). 43 , 44 We have obtained unambiguous support for the structures of 5k′ using X-ray crystallographic analysis (see CYLviews in Figure 5 E).…”

Section: Resultsmentioning

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: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

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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“…Moreover, we examined the DA reaction of 1-boron-diene 28,37 E-3k with gem-diborylalkene 2, and surprisingly, the reaction generated the rare 1,1,2-triboryl cyclic adduct 4k as the exclusive isomer with complete stereospecificity (Figure 3E). 12,37,38 We have obtained unambiguous support for the structures of 4k using X-ray crystallographic analysis (see CYLviews in Figure 3E). Theoretical calculations indicate that the TS of the 1,1,2 triboryl constitutional isomer is favored by 3 Kcal/mol over the TS of 1,1,3 triboryl isomer (1,1,2-triBpin-TS vs 1,1,3 triBpin-Ts; Figure 3F).…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, the DA reaction of 1-boron-diene 28,37 (E-3k) with gem-diborylalkene 2' generated regioselectively the separable diastereomers of 1,1,2-triboryl cyclic adduct with complete stereospecificity (5k, 5k'; Figure 4G). 37,38 We have obtained unambiguous support for the structures of 5k' using X-ray crystallographic analysis (see CYLviews in Figure 4G). Additionally, the reaction of 2' with 3,4 diboryl diene 3l yielded 1,1,3,4 tetraborylcyclohexene adduct 5l (Figure 4F).…”

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>

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Organoboron Compounds Towards Asymmetric Pericyclic Reaction; Exploitation to Bioactive Molecule Synthesis

et al. 2022

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Organic frameworks containing boron as one of the units have wide application in organic synthesis. Due to the non‐toxicity and cheap accessibility, the organoboron compounds have gained increased demand towards the organic chemist. Besides, there has been a huge progress in the area of chiral organoboron synthesis, which allows direct access to chiral synthons. Among other methods developed for the asymmetric synthesis of organoboron compounds, pericyclic reaction plays an important role. Cycloaddition reactions using vinyl boronic esters have been extensively reported for the synthesis of cyclic boronic esters. Asymmetric cycloaddition using organoboron compound opens a quick access to various intermediates with multiple chiral centers, which has been utilized for the total synthesis of bioactive molecules. This mini‐review outlines various asymmetric pericyclic reactions developed to date demonstrating its applicability towards bioactive molecule synthesis.

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Generating Skeletal Diversity and Complexity from Boron‐Substituted 1,3‐Dienes and Enophiles

Cited by 6 publications

References 97 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

Organoboron Compounds Towards Asymmetric Pericyclic Reaction; Exploitation to Bioactive Molecule Synthesis

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