Highly diastereoselective approach to methylenecyclopropanes via boron-homologation/allylboration sequences

Baumann, Andreas N.; Music, Arif; Karaghiosoff, Konstantin; Didier, Dorian

doi:10.1039/c5cc09904h

Cited by 16 publications

(10 citation statements)

References 36 publications

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“…We recently reported an efficient method for the diastereo‐ and enantioselective preparation of alkylidenecyclopropanes and ACBs . Our general approach is based on a one‐pot boron‐homologation/allylboration sequences.…”

Section: Resultsmentioning

confidence: 99%

“…= 161.5 (d, J = 245.5 Hz), 142.3 (d, J = 2.3 Hz), 134 8,. 132.8 (d, J = 3.2 Hz), 127.1 (d, J = 7.8 Hz), 115.3 (d, J = 21.4 Hz), 41.9, 33.0, 32.9, 32.3, 27.4, 22.9, 14.3, 14.2. ppm;I R: ñ = 2957 (m), 2923 (m), 2855 (m), 1655 (vw), 1601 (w), 1507 (vs), 1467 (w), 1408 (vw), 1376 (w), 1324 (w), 1294 (w), 1230 (s), 1182 (vw), 1155 (m), 1104 (w), 1069 (vw), 1012 cm À1 (vw);H RMS (EI): m/z calcd for C 16 H 21 F + :2 32.1627; found:232.1624.Compounds 20 c-j:S ee the Supporting Information.…”

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confidence: 99%

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Unsaturated Four‐Membered Rings: Efficient Strategies for the Construction of Cyclobutenes and Alkylidenecyclobutanes

Eisold

Baumann

Kiefl

et al. 2016

Chemistry A European J

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Our recent studies of the diastereo- and enantioselective formation of strained alkylidenecycloalkanes drove us to more-thoroughly investigate the formation of four-membered rings for which only few efficient methods are described. We first developed a strategy to diversify the saturated part of the four-membered ring and applied it to a highly diastereoselective synthesis of more-elaborate alkylidenecyclobutanes, which completed our precedent studies. In parallel, cyclobutene structures were built employing simple organometallic methods and further functionalized to give a diverse range of new substitution patterns, which consequently enriched the pool of cyclobutene-based building blocks.

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

Unsaturated Four‐Membered Rings: Efficient Strategies for the Construction of Cyclobutenes and Alkylidenecyclobutanes

Eisold

Baumann

Kiefl

et al. 2016

Chemistry A European J

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“…Additionally, Didier et al reported the allylboration reaction of cyclopropenylmethylboronic esters such as 153 with aldehydes [Scheme 34 (c)]. 72 By this reaction, highly substituted allyl alcohols were prepared with fine control over regioselectivity, according to the boron-induced polarization, as well as on diastereoselectivity, which is governed by sterics. 73…”

Section: Miscellanea Of Reactionsmentioning

confidence: 99%

Recent Progresses towards the Strengthening of Cyclopropene Chemistry

Vicente

2016

Synthesis

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This short review focuses on the most relevant achievements in the field of cyclopropene chemistry including their syntheses, reactivities, and applications. As the chemistry of cyclopropenes has rapidly evolved in the last few years, valuable implementations on synthetic approaches are nowadays available. Moreover, exciting and useful applications by means of cyclopropenes in organic synthesis and other research areas have also been disclosed. Herein, an overview covering advances accomplished from 2011 until the beginning of 2016 is presented. 1 Introduction 2 Progress on Cyclopropene Syntheses 3 Reactivity of Cyclopropenes 3.1 Carbometalations and Related Reactions 3.2 Cycloisomerizations to Furan Derivatives and Related Reactions 3.3 Cyclopropene Isomerization to Vinyl Carbene Intermediates 3.4 Miscellanea of Reactions 4 Applications of Cyclopropenes 5 Conclusion Key words catalysis, cyclopropenes, cyclopropanes, ring strain, synthesis Rubén Vicente studied chemistry at the Complutense University in Madrid. He obtained his Ph.D. from the University of Oviedo in 2006 with Prof. J. Barluenga, developing synthetic applications of Fischer carbenes. After short research stays at the University of Bonn and Boston College, he spent three years as a Postdoctoral Researcher sponsored by the Humboldt Foundation in the group of Prof. L. Ackermann (Georg-August-Universität, Göttingen, 2007-2009), working on C-H bond functionalizations. He returned to Oviedo in 2010 within the 'Juan de la Cierva' program and since 2012 he has held a 'Ramón y Cajal' Fellowship. In 2014, he was awarded with the Young Investigator Award from the Spanish Royal Chemical Society. His interests include the discovery of new reactivity patterns and sustainable catalysis.

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“…Examples of those transformations include the carboxylation of a (trimethylsilylmethyl)cyclopropene in the presence of a fluoride promoter [22], and also the addition of electrophiles to (lithiomethyl)cyclopropenes generated by lithiation of the corresponding methylcyclopropenylsulfone [23] or -sulfoxide [24]. More recently, the addition of cyclopropenylmethylboronates to aldehydes was also reported [25]. A complementary strategy involves the addition of nucleophiles, in particular organometallic reagents, to cyclopropenylcarbinols or their derivatives E , which leads to alkylidenecyclopropanes F through a formal S N 2’ process (Scheme 1, reaction 3) [23,26–33].…”

Section: Introductionmentioning

confidence: 99%

Sigmatropic rearrangements of cyclopropenylcarbinol derivatives. Access to diversely substituted alkylidenecyclopropanes

Ernouf¹,

Brayer²,

Meyer³

et al. 2019

Beilstein J. Org. Chem.

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Cyclopropenes constitute useful precursors of other classes of compounds incorporating a three-membered ring. Although the transformation of substituted cyclopropenes into alkylidenecyclopropanes can be accomplished through different strategies, this review is focusing specifically on the use of [2,3]- and [3,3]-sigmatropic rearrangements involving cyclopropenylcarbinol derivatives as substrates. These sigmatropic rearrangements, which have been developed in recent years, allow a remarkably efficient and stereoselective access to a wide variety of heterosubstituted and/or functionalized alkylidenecyclopropanes which would not be readily accessible by other strategies. The different [2,3]- and [3,3]-sigmatropic rearrangements of cyclopropenylcarbinol derivatives disclosed to date, as well as the analysis of their substrate scope and some applications of the products arising from those reactions, are presented in this review.

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Highly diastereoselective approach to methylenecyclopropanes via boron-homologation/allylboration sequences

Cited by 16 publications

References 36 publications

Unsaturated Four‐Membered Rings: Efficient Strategies for the Construction of Cyclobutenes and Alkylidenecyclobutanes

Unsaturated Four‐Membered Rings: Efficient Strategies for the Construction of Cyclobutenes and Alkylidenecyclobutanes

Recent Progresses towards the Strengthening of Cyclopropene Chemistry

Sigmatropic rearrangements of cyclopropenylcarbinol derivatives. Access to diversely substituted alkylidenecyclopropanes

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