Cycloalkenylboranes as Highly Reactive and Selective Diels−Alder Dienophiles. A Simple Synthesis of Bridgehead Bicyclic Alcohols

Lee, Yu-Kai; Singleton, Daniel A.

doi:10.1021/jo9619701

Cited by 33 publications

(8 citation statements)

References 16 publications

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“…[102][103][104] Similar enhanced reactivity was discovered for alkenyldihaloboron derivatives (Scheme 53). [105][106][107][108] The major drawback of both types of the dienophiles is their limited stability, which prompts their generation in situ. Neverthe-less, their utility as enol and enamine synthetic equivalents, as well as for the preparation of the corresponding boropinacolates was demonstrated successfully.…”

Section: Scheme 51mentioning

confidence: 99%

Cycloadditions of Alkenylboronic Derivatives

et al. 2020

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The literature on cycloaddition reactions of boron-containing alkenes is surveyed with 132 references. The data are categorized according to the reaction type ([2+1], [2+2], [3+2], [4+2], and [4+3] cycloadditions). The cyclopropanation and the Diels–Alder reactions of alkenylboronic derivatives have been studied more or less comprehensively, and for some substrates, they can be considered as convenient methods for the rapid regio- and stereoselective construction of even complex cyclic systems. Other types of the cycloadditions, as well as mechanistic aspects of the processes, have been addressed less thoroughly in the previous works.1 Introduction2 [2+1] Cycloaddition2.1 Cyclopropanation2.1.1 With Methylene Synthetic Equivalents2.1.2 With Substituted Carbenoids2.2 Epoxidation2.3 Aziridination3 [2+2] Cycloaddition4 [3+2] Cycloaddition4.1 With Nitrile Oxides4.2 With Diazoalkanes4.3 With Nitrones4.4 With Azomethine Ylides5 [4+2] Cycloaddition6 [4+3] Cycloaddition7 Conclusions and Outlook

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Section: Scheme 51mentioning

confidence: 99%

Cycloadditions of Alkenylboronic Derivatives

et al. 2020

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“…Subsequently, in the reactions with acyclic 1,3-dienes, bicyclic derivatives of type 94 were obtained after oxidative work-up. 53 The dienophiles 93a and 93b are far more reactive compared to other cyclic dienophiles with non-boron acceptor substituents. Thus, the cycloaddition proceeds at room temperature within a few hours.…”

Section: Scheme 33mentioning

confidence: 99%

Boron-Substituted Building Blocks in Diels-Alder and Other Cycloaddition Reactions

Hilt¹,

Bolze²

2005

Synthesis

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Boron-containing building blocks are among the most prominent starting materials in several transformations based on their wide range of synthetic applications. Over the last decade various cycloaddition reactions were reported where boron-containing 1,3-dienes or boron-containing dienophiles were used. Combined with the broad follow-up chemistry, target-oriented as well as diversity-oriented syntheses could be established.

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“…In the past decades, Singleton and others have extensively explored the synthetic utility of alkenyl-, alkynyl-and dienylboranes in Diels-Alder reactions. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] Given that many variations of the Diels-Alder reaction of vinylboranes have been developed, it is surprising that there is only one precedent in the use of chiral vinylboranes in asymmetric [4 + 2] cycloaddition reactions. This Diels-Alder reaction was based on the use of dialkylvinylborane 1, derived from (+)-camphene, with 2-phenyl-1,3-butadiene (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Alkylhalovinylboranes: a new class of Diels–Alder dienophiles

Pisano

Pellegrinet

2018

RSC Adv.

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The Diels-Alder reactions of alkylhalovinylboranes have been investigated theoretically and experimentally. Alkylhalovinylboranes presented higher reactivity than the corresponding dialkylvinylboranes. Although endo/exo selectivities were high for the reactions with cyclopentadiene, facial selectivities for the chiral analogues were low. Our results demonstrate that the replacement of an alkyl group on the boron atom by a halogen increases the dienophilicity considerably.Scheme 1 Synthesis and Diels-Alder reaction of chiral dialkylvinylborane 1. † Electronic supplementary information (ESI) available: Experimental section, NMR spectra, computational methods, FMOs and global and local reactivity indices of reactants, optimized geometries of the transition structures (TSs) not included in the paper and charge transfer (GEDT) of TSs, cartesian coordinates, absolute energies including zero-point energy corrections, free energies and number of imaginary frequencies of all the stationary points reported in the paper and values of imaginary frequencies of all transition structures. See

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Cycloalkenylboranes as Highly Reactive and Selective Diels−Alder Dienophiles. A Simple Synthesis of Bridgehead Bicyclic Alcohols

Cited by 33 publications

References 16 publications

Cycloadditions of Alkenylboronic Derivatives

Cycloadditions of Alkenylboronic Derivatives

Boron-Substituted Building Blocks in Diels-Alder and Other Cycloaddition Reactions

Alkylhalovinylboranes: a new class of Diels–Alder dienophiles

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