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Search for "organolithium" in Full Text gives 74 result(s) in Beilstein Journal of Organic Chemistry.
(E,Z)-1,1,1,4,4,4-Hexafluorobut-2-enes: hydrofluoroolefins halogenation/dehydrohalogenation cascade to reach new fluorinated allene
Beilstein J. Org. Chem. 2024, 20, 452–459, doi:10.3762/bjoc.20.40
- continues to be relevant. One of the methods for the synthesis of allenes was based on the interaction of bromoolefins with organolithium compounds, followed by the elimination of lithium fluoride [29][30][31]. It was logical to assume that in our case a similar reaction of the Grignard reagent 12 with
Beyond n-dopants for organic semiconductors: use of bibenzo[d]imidazoles in UV-promoted dehalogenation reactions of organic halides
Beilstein J. Org. Chem. 2023, 19, 1912–1922, doi:10.3762/bjoc.19.142
- bibenzyls being the dominant products. These reaction conditions represent an alternative metal-free approach to the conventional synthesis of bibenzyls through the reaction of Grignard or organolithium reagents with benzyl halides, or to the use of highly active metal reagents [33][34][35][36] or metal
Application of N-heterocyclic carbene–Cu(I) complexes as catalysts in organic synthesis: a review
Beilstein J. Org. Chem. 2023, 19, 1408–1442, doi:10.3762/bjoc.19.102
- selective method for the synthesis of a wide range of organic compounds [55][56]. Organometallic reagents, such as organolithium, organomagnesium, and organozinc reagents are commonly used in conjugate addition reactions. 2.2.1 Reaction with Grignard reagents: Organomagnesium reagents, such as Grignard
- , have also been employed in conjugate addition reactions. These reagents are less reactive than organolithium and Grignard reagents but can still add to a range of α,β-unsaturated carbonyl compounds, including enones, acrylates, and imines. In 2011 Sakaguchi and co-worker [64] accomplished the conjugate
Enolates ambushed – asymmetric tandem conjugate addition and subsequent enolate trapping with conventional and less traditional electrophiles
Beilstein J. Org. Chem. 2023, 19, 593–634, doi:10.3762/bjoc.19.44
- diastereomers were detected (Scheme 9A). Furthermore, the authors have also demonstrated a four-component coupling reaction: by simply increasing the amount of the organolithium reagent (2.05 equiv) used for the activation of the Zn enolate, β-hydroxyketones 40 were gained via 1,2-addition of the zincate
Modern flow chemistry – prospect and advantage
Beilstein J. Org. Chem. 2023, 19, 33–35, doi:10.3762/bjoc.19.3
- mass transfer of continuous flow reactors. The generation of organolithium species in the presence of carbonyl compounds and their reaction has been facilitated by the extremely fast mixing of reagents and almost instantaneous heat transfer (i.e., cooling) in specifically designed microreactors [5
Total synthesis of grayanane natural products
Beilstein J. Org. Chem. 2022, 18, 1707–1719, doi:10.3762/bjoc.18.181
- proposes different disconnections. Newhouse identified a C1–C10 disconnection for a radical cyclization and a C6–C7 for an organolithium addition, allowing a convergent approach with A ring and C–D rings as key fragments. In this case, the bicyclo[3.2.1]octane is obtained by a Ni-catalyzed enolate/alkenyl
Preparation of an advanced intermediate for the synthesis of leustroducsins and phoslactomycins by heterocycloaddition
Beilstein J. Org. Chem. 2022, 18, 1385–1395, doi:10.3762/bjoc.18.143
- fragment was accomplished in a stereoselective fashion through a vinyllithium intermediate. An advanced synthetic intermediate was then obtained after functional group transformation. Keywords: cycloaddition; organolithium; stereoselective; total synthesis; Introduction Leustroducsins 1a–c and
- considered the use of additives in order to make the organolithium intermediate more nucleophilic. However, no reaction was observed when ZnMe2 (which was used in the synthesis of leustroducsin B by Trost and co-workers [17]) was added; trimethylaluminum and cerium chloride also failed to promote the
Modular synthesis of 2-furyl carbinols from 3-benzyldimethylsilylfurfural platforms relying on oxygen-assisted C–Si bond functionalization
Beilstein J. Org. Chem. 2022, 18, 1256–1263, doi:10.3762/bjoc.18.131
- biomass-derived furfural and 5-methylfurfural, are converted into 3-silylated 2-furyl carbinols upon condensation with organomagnesium or organolithium reagents. The hydroxy unit of the carbinol adducts can be exploited to promote C3(sp2)–Si bond functionalization through intramolecular activation. Two
- and Discussion Synthesis of 3-silylated 2-furyl carbinols C3-silylated furfurals 1a–c and 2c are accessible from furfural or 5-methylfurfural [20], respectively, according to our previously reported protocol for selective catalytic C3 silylation [15]. The addition of organolithium [21] or Grignard
Synthesis of novel alkynyl imidazopyridinyl selenides: copper-catalyzed tandem selenation of selenium with 2-arylimidazo[1,2-a]pyridines and terminal alkynes
Beilstein J. Org. Chem. 2022, 18, 863–871, doi:10.3762/bjoc.18.87
- inexpensive and easy to handle Se powder as the Se source. The reaction proceeded with terminal alkynes having various substitutions, such as aryl, vinyl, and alkyl groups. The obtained alkynyl imidazopyridinyl selenide was found to undergo nucleophilic substitution reaction on Se atom using organolithium
Allylic alcohols and amines by carbenoid eliminative cross-coupling using epoxides or aziridines
Beilstein J. Org. Chem. 2021, 17, 2385–2389, doi:10.3762/bjoc.17.155
- , α-methoxyhexyllithium derived from stannane 7 [14][15] was reacted with terminal epoxide 5, which gave the allylic alcohol 8 (79%, E/Z = 73:27, Scheme 4). This organolithium also proved reactive with 2,2-disubstituted epoxide 9, giving allylic tertiary alcohol 10 (72%, E/Z = 82:18). A trisubstituted
N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles
Beilstein J. Org. Chem. 2021, 17, 1096–1140, doi:10.3762/bjoc.17.86
- reactions using organolithium and organocerium compounds. In some examples, the use of organolithium is feasible through the use of aluminum-derived additives [15]. In this study, the influence of solvents on diastereoselectivity was also observed. They found that the reactions performed in noncoordinating
- mechanism operating in reactions involving Grignard reagents in noncoordinating solvents, such as toluene and dichloromethane, while an acyclic model [43] is common in organolithium compounds in solvents such as THF. In the cyclic model, the bulky tert-butyl group occupies an equatorial position due to
A sustainable strategy for the straightforward preparation of 2H-azirines and highly functionalized NH-aziridines from vinyl azides using a single solvent flow-batch approach
Beilstein J. Org. Chem. 2021, 17, 203–209, doi:10.3762/bjoc.17.20
- preparation of 2H-azirines and their stereoselective transformation into highly functionalized NH-aziridines, starting from vinyl azides and organolithium compounds. The protocol has been developed using cyclopentyl methyl ether (CPME) as an environmentally benign solvent, resulting into a sustainable, safe
- and potentially automatable method for the synthesis of interesting strained compounds. Keywords: aziridines; 2H-azirines; flow chemistry; green chemistry; organolithium compounds; Introduction Since their conception in the early 1990s, Green Chemistry Principles (GCP) have been applied with
- to access aziridines with great structural variability [21]. The reaction of azirines with Grignard and organolithium reagents has been poorly investigated, and only without using green and renewable solvents [22][23]. In turn, 2H-azirines can be smoothly obtained through intramolecular cyclization
Disposable cartridge concept for the on-demand synthesis of turbo Grignards, Knochel–Hauser amides, and magnesium alkoxides
Beilstein J. Org. Chem. 2020, 16, 1343–1356, doi:10.3762/bjoc.16.115
- flow system). We predict that with small modifications, this system could be configured to produce many different reagents. Our group is currently working on an organolithium version of this on-demand reagent approach. Experimental Turbo Grignard: isopropylmagnesium chloride–lithium chloride complex
Oxime radicals: generation, properties and application in organic synthesis
Beilstein J. Org. Chem. 2020, 16, 1234–1276, doi:10.3762/bjoc.16.107
- organolithium reagents 41 at 0 °C in Et2O forming mainly di-tert-butyl oxime 1f and the products of C–O coupling [86]. The reactions were performed by addition of the solution of the organometallic compound 41 in Et2O to the solution of di-tert-butyliminoxyl radical in Et2O. The product yields obtained
- employing organolithium reagents are presented below (Scheme 14). The Grignard reagents demonstrated very similar results that are omitted. Among the major C–O coupling product (oxime ether 42) small amounts of C–N coupling products (nitrones 43) were detected in the case of sterically unhindered
- organolithium reagents. Presumably, the reaction proceeds via SET from the organometallic compound and iminoxyl radical with the formation of an oxime anion and an intermediate C-centered radical. In the case of MeLi and PhLi, which correspond to the most reactive methyl and phenyl radicals, products 44 of
Copper-catalysed alkylation of heterocyclic acceptors with organometallic reagents
Beilstein J. Org. Chem. 2020, 16, 1006–1021, doi:10.3762/bjoc.16.90
- heterocyclic ring, while the second part deals with acceptors in which the reacting unsaturated double bond is located outside of the heterocyclic unit (e.g., alkenyl-substituted heterocycles). The organometallics discussed in this minireview include organoaluminium, organozinc, organozirconium, organolithium
- -catalysed AAAs using Grignard, organolithium, organoaluminium, and organozirconium reagents have been reported. In 2015, Fletcher and co-workers presented the copper-catalysed AAA of racemic 3,6-dihydro-2H-pyrans using alkylzirconocenes in the presence of the Cu/L14 catalytic system (Scheme 10A) [39
- co-workers elaborated the copper-catalysed ring opening reaction of oxabicyclic alkene substrates using organolithium reagents, finding excellent anti selectivities and enantioselectivity (Scheme 12) [42]. During the optimisation studies, they discovered that when the Lewis acid BF3·OEt2 was employed
Synthesis of six-membered silacycles by borane-catalyzed double sila-Friedel–Crafts reaction
Beilstein J. Org. Chem. 2020, 16, 409–414, doi:10.3762/bjoc.16.39
- in terms of the functional group tolerance and versatility of these previously reported synthetic methods due to the use of a stoichiometric amount of the organolithium reagents. In addition, despite these contributions, catalytic reaction systems have not been developed as much [26][27]. The sila
Architecture and synthesis of P,N-heterocyclic phosphine ligands
Beilstein J. Org. Chem. 2020, 16, 362–383, doi:10.3762/bjoc.16.35
- where the metalated organohalogen compound is reacted with the halogen phosphine. Alternatively, the metal phosphide can be reacted with an organohalogen compound leading to the desired product. The most commonly used trans-metalation reagents are Grignard [54] or organolithium reagents [55] and other
- to the coordinating phosphorous [79]. The PTA-PPh2 ligand 76 is derived from the lithiated intermediate 75 (Scheme 14) [79]. The conversion of PTA (74) to the organolithium intermediate (PTA-Li, 75) is almost quantitative with a 90% isolated yield. However, the yield of the desired ligand PTA-PPh2 76
Allylic cross-coupling using aromatic aldehydes as α-alkoxyalkyl anions
Beilstein J. Org. Chem. 2020, 16, 185–189, doi:10.3762/bjoc.16.21
- , agrochemicals and bioactive natural products. Generally, α-alkoxyalkyl anions are presynthesized as stoichiometric organometallic reagents such as organolithium, organozinc, organocuprate, organostannane, organosilane and organoboron compounds [1][2][3][4][5][6]. Alternatively, we showed that easily available
Functionalization of 4-bromobenzo[c][2,7]naphthyridine via regioselective direct ring metalation. A novel approach to analogues of pyridoacridine alkaloids
Beilstein J. Org. Chem. 2019, 15, 2304–2310, doi:10.3762/bjoc.15.222
- amphimedine (1) [11]. 4-Chloro-5-methylbenzo[c][2,7]naphthyridine (8) was oxidized at the methyl group to give an aldehyde. Subsequent modifications of the formyl group and Stille couplings at C-4 gave a number of 4,5-disubstituted benzo[c][2,7]naphthyridines (Figure 2A) [12]. Organolithium compounds were
- ring metalation of 4-bromobenzo[c][2,7]naphthyridine (9d) the choice of an appropriate base was essential. Alkyllithium bases were not suitable, since two undesired reactions were anticipated: As mentioned above, 4-substituted benzo[c][2,7]naphthyridines tend to add organolithium compounds to the C-5
Efficient synthesis of pyrazolopyridines containing a chromane backbone through domino reaction
Beilstein J. Org. Chem. 2019, 15, 874–880, doi:10.3762/bjoc.15.85
- products 5a–d were not formed. The reaction mechanism is shown in Scheme 2. The chemical structures of the products 5a–d are shown in Figure 4. Usually, to activate the nitrile group for cyclization reaction, the existence of Lewis acid, the addition of organolithium reagents or metal
Diastereo- and enantioselective preparation of cyclopropanol derivatives
Beilstein J. Org. Chem. 2019, 15, 752–760, doi:10.3762/bjoc.15.71
- ). First, we checked that the carbometalation reaction was regio- and diastereoselective by addition of lower order cyanocuprate, easily obtained from the corresponding organolithium and a stoichiometric amount of CuCN (Scheme 4) [68][69][70]. The addition reaction proceeds similarly for the addition of
Synthesis and biological investigation of (+)-3-hydroxymethylartemisinin
Beilstein J. Org. Chem. 2019, 15, 567–570, doi:10.3762/bjoc.15.51
- -hydroxymethylartemisinin (2, Figure 1). Results and Discussion Our synthesis (Scheme 1) started from the known and readily available aldehyde 3 [14] which was treated with the organolithium species obtained from derivative 4 [15] and n-BuLi to yield derivative 5. The latter afforded allylic alcohol 6 after reduction of
Sigmatropic rearrangements of cyclopropenylcarbinol derivatives. Access to diversely substituted alkylidenecyclopropanes
Beilstein J. Org. Chem. 2019, 15, 333–350, doi:10.3762/bjoc.15.29
- chiral phosphines possessing an alkylidenecyclopropane backbone [34]. The starting cyclopropenylcarbinols were readily prepared by addition of the corresponding cyclopropenyl organolithium reagents, generated in situ by treatment of 1,1,2-tribromocyclopropane with n-butyllithium (2 equiv) [35], to
Practical tetrafluoroethylene fragment installation through a coupling reaction of (1,1,2,2-tetrafluorobut-3-en-1-yl)zinc bromide with various electrophiles
Beilstein J. Org. Chem. 2018, 14, 2375–2383, doi:10.3762/bjoc.14.213
- that possesses higher thermal stability than the corresponding organolithium or -magnesium species due to the almost covalent C–Zn bond [29][30]. Moreover, organozinc reagents can be easily transformed to the “reactive” species, through a transmetallation process with a transition metal (e.g., Pd or Cu
Evaluation of dispersion type metal···π arene interaction in arylbismuth compounds – an experimental and theoretical study
Beilstein J. Org. Chem. 2018, 14, 2125–2145, doi:10.3762/bjoc.14.187
- a monoclinic form 2b, both were obtained from iPrOH solution. In order to develop a better understanding with regard to the effects of substituents, (C6H4-OMe-4)3Bi (3) [50][51] was prepared starting from BiCl3 and the corresponding organolithium reagent following a general method as reported by
- . Finally its chloro derivative (C6H3-t-Bu2-3,5)2BiCl (5) was synthesized in 11% yield using the organolithium derivative (C6H3-t-Bu2-3,5)Li and BiCl3. This series of compounds and polymorphs (Scheme 1) allows to deduce some general trends regarding dispersion type interactions including bismuth···π, π···π
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