Cross metathesis of unsaturated epoxides for the synthesis of polyfunctional building blocks

• Meriem K. Abderrezak,
• Kristýna Šichová,
• Nancy Dominguez-Boblett,
• Antoine Dupé,
• Zahia Kabouche,
• Christian Bruneau and
• Cédric Fischmeister

Beilstein J. Org. Chem. 2015, 11, 1876–1880, doi:10.3762/bjoc.11.201

• double bond transformations by olefin metathesis have significantly impacted organic and polymer synthesis over the last two decades [1][2][3]. If early works focused on ring-closing metathesis and ring-opening metathesis polymerization, progresses in catalysts performances [4][5] and selectivity have

Recent applications of ring-rearrangement metathesis in organic synthesis

• Sambasivarao Kotha,
• Milind Meshram,
• Priti Khedkar,
• Shaibal Banerjee and
• Deepak Deodhar

Beilstein J. Org. Chem. 2015, 11, 1833–1864, doi:10.3762/bjoc.11.199

• (ROM)/ring-closing metathesis (RCM) in a one-pot operation to generate complex targets. RRM delivers complex frameworks that are difficult to assemble by conventional methods. The noteworthy point about this type of protocol is multi-bond formation and it is an atom economic process. In this review, we

• decades have changed the landscape of organic synthesis. Armed with these advances, olefin metathesis has become a staple in retrosynthesis. Metathesis protocols such as ring-closing metathesis (RCM), cross-metathesis (CM), and enyne metathesis (EM) have gained popularity in the synthesis of complex

Nitro-Grela-type complexes containing iodides – robust and selective catalysts for olefin metathesis under challenging conditions

• Andrzej Tracz,
• Mateusz Matczak,
• Katarzyna Urbaniak and
• Krzysztof Skowerski

Beilstein J. Org. Chem. 2015, 11, 1823–1832, doi:10.3762/bjoc.11.198

• Iodide-containing nitro-Grela-type catalysts have been synthesized and applied to ring closing metathesis (RCM) and cross metathesis (CM) reactions. These new catalysts have exhibited improved efficiency in the transformation of sterically, non-demanding alkenes. Additional steric hindrance in the

• - analogues of HII, but no improvement was noted [13][14][15]. Moreover, the presence of iodide ligands reduced initiation rates for Hoveyda second generation complex bearing iodides (HII-I2) in ring-closing metathesis (RCM). Similarly, Schrodi and colleagues did not find any advantages for halide exchanged

Preparation of conjugated dienoates with Bestmann ylide: Towards the synthesis of zampanolide and dactylolide using a facile linchpin approach

• Jingjing Wang,
• Samuel Z. Y. Ting and
• Joanne E. Harvey

Beilstein J. Org. Chem. 2015, 11, 1815–1822, doi:10.3762/bjoc.11.197

• aldehyde fragment 6 by asymmetric alkynylation, and form the pyran using an oxa-Michael addition, in a manner reminiscent of that employed by Uenishi and co-workers [34]. Finally, macrocyclisation will be achieved through the well-established strategy of ring-closing metathesis at C8–C9. Results and

Grubbs–Hoveyda type catalysts bearing a dicationic N-heterocyclic carbene for biphasic olefin metathesis reactions in ionic liquids

• Maximilian Koy,
• Hagen J. Altmann,
• Benjamin Autenrieth,
• Wolfgang Frey and
• Michael R. Buchmeiser

Beilstein J. Org. Chem. 2015, 11, 1632–1638, doi:10.3762/bjoc.11.178

• activity of Ru-2 compared to standard Grubbs- and Grubbs–Hoveyda catalysts. Thus, Ru-2 delivers only turn-over numbers well below 100 in the biphasic ring-closing metathesis (RCM) of 1,7-octadiene, diethyl diallylmalonate and N,N-diallyl p-toluoenesulfonamide using [BDMIM+][BF4−] as IL and toluene as the

Latent ruthenium–indenylidene catalysts bearing a N-heterocyclic carbene and a bidentate picolinate ligand

• Thibault E. Schmid,
• Florian Modicom,
• Adrien Dumas,
• Etienne Borré,
• Loic Toupet,
• Olivier Baslé and
• Marc Mauduit

Beilstein J. Org. Chem. 2015, 11, 1541–1546, doi:10.3762/bjoc.11.169

• -diisopropylphenyl)imidazolidin-2-ylidene) demonstrated excellent latent behaviour in ring closing metathesis (RCM) reaction and could be activated in the presence of a Brønsted acid. The versatility of the catalyst 4a was subsequently demonstrated in RCM, cross-metathesis (CM) and enyne metathesis reactions

• in model ring closing metathesis and cross-metathesis transformations. Results and Discussion With the objective to develop an attractive strategy for the synthesis of indenylidene-picolinic ruthenium complexes, we initially attempted their preparation using a silver-free methodology. In fact, silver

Ruthenium indenylidene “1^st generation” olefin metathesis catalysts containing triisopropyl phosphite

• Stefano Guidone,
• Fady Nahra,
• Alexandra M. Z. Slawin and
• Catherine S. J. Cazin

Beilstein J. Org. Chem. 2015, 11, 1520–1527, doi:10.3762/bjoc.11.166

• polymerization on demand through use of a stimulus [35][36]. The use of this catalyst in the ring-closing metathesis (RCM) reaction gave excellent conversions of challenging substrates, even at low catalyst loadings. The high activity and robustness of cis-Caz-1 is derived from synergistic effects between the σ

• ring-closing metathesis (RCM) The reactivity of the mixed phosphine/phosphite complex 1 was first evaluated in the RCM of the easily cyclized diethyl diallylmalonate (4) (see Supporting Information File 1, section 2). The need for thermal activation for this pre-catalyst was clearly revealed by the low

Design and synthesis of hybrid cyclophanes containing thiophene and indole units via Grignard reaction, Fischer indolization and ring-closing metathesis as key steps

• Sambasivarao Kotha,
• Ajay Kumar Chinnam and
• Mukesh E. Shirbhate

Beilstein J. Org. Chem. 2015, 11, 1514–1519, doi:10.3762/bjoc.11.165

• via Grignard addition, Fischer indolization and ring-closing metathesis as key steps. Keywords: cyclophane; Grignard reaction; Fischer indolization; ring-closing metathesis; Introduction Modern olefin metathesis catalysts enable a late stage ring-closing step starting with bisolefinic substrates

• containing polar functional groups [1]. As part of a major program aimed at developing new and intricate strategies to cyclophanes [2][3][4][5][6][7][8][9][10], we envisioned various building blocks [11] by ring-closing metathesis (RCM) as a key step [12][13][14][15][16][17][18][19][20][21][22][23][24][25

Synthesis of a tricyclic lactam via Beckmann rearrangement and ring-rearrangement metathesis as key steps

• Sambasivarao Kotha,
• Ongolu Ravikumar and
• Jadab Majhi

Beilstein J. Org. Chem. 2015, 11, 1503–1508, doi:10.3762/bjoc.11.163

• metathetic transformations such as ring-closing metathesis (RCM) and ring-opening metathesis (ROM). The RRM has emerged as a powerful tool in organic synthesis because of its ability to transform simple starting materials into complex targets involving an ingenious design. The retrosynthetic strategy to the

Tandem cross enyne metathesis (CEYM)–intramolecular Diels–Alder reaction (IMDAR). An easy entry to linear bicyclic scaffolds

• Javier Miró,
• María Sánchez-Roselló,
• Álvaro Sanz,
• Fernando Rabasa,
• Carlos del Pozo and
• Santos Fustero

Beilstein J. Org. Chem. 2015, 11, 1486–1493, doi:10.3762/bjoc.11.161

• the ring closing metathesis (RCM) of 2a), and unreacted 2a. The isolated yield of 3a was improved to 57% by increasing the reaction time to 48 hours (Table 1, entries 2 and 3). An extended reaction time (72 h) led to a drop in the final yield (Table 1, entry 4). In all cases variable amounts of 4a

Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

• Karolina Żukowska,
• Eva Pump,
• Aleksandra E. Pazio,
• Krzysztof Woźniak,
• Luigi Cavallo and
• Christian Slugovc

Beilstein J. Org. Chem. 2015, 11, 1458–1468, doi:10.3762/bjoc.11.158

• reactivity of the complexes. Keywords: DFT calculations; olefin metathesis; ring closing metathesis; ring-opening metathesis polymerisation; ruthenium; Introduction Olefin metathesis is a catalytic process during which C–C double bonds are exchanged [1]. Since the first examples were published in the 1950s

• research was devoted to exploring the activity of the obtained complexes in metathesis reactions. The preliminary choice was to conduct ring-closing metathesis (RCM) of diethyl diallylmalonate (16, Scheme 4). Initially examined conditions (DCM, rt) originate from the papers previously published by Grela’s

Spiro annulation of cage polycycles via Grignard reaction and ring-closing metathesis as key steps

• Sambasivarao Kotha,
• Mohammad Saifuddin,
• Rashid Ali and
• Gaddamedi Sreevani

Beilstein J. Org. Chem. 2015, 11, 1367–1372, doi:10.3762/bjoc.11.147

• -pyrano cage compound 7 involving ring-closing metathesis is reported. The hexacyclic dione 10 was prepared from simple and readily available starting materials such as 1,4-naphthoquinone and cyclopentadiene. The synthesis of an unprecedented octacyclic cage compound through intramolecular Diels–Alder (DA

• ) reaction as a key step is described. The structures of three new cage compounds 7, 12 and 18 were confirmed by single crystal X-ray diffraction studies. Keywords: cage molecules; Diels–Alder reaction; Grignard reaction; ring-closing metathesis; spirocycles; Introduction Design and synthesis of

• -closing metathesis (RCM) are considered as viable options. The retrosynthetic analysis to the target bis-spiro-cage compound 7 is shown in Figure 2. The target compound 7 could be obtained from O-allylation of the Grignard addition product 11 followed by the two-fold RCM sequence. The required cage dione

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

• agents in the presence of Cu(II). Fürstner and co-workers [72] have reported the total synthesis of natural products 22–24 by using a metathesis reaction [73][74][75][76][77][78][79][80][81][82] as the key step. The ring-closing metathesis (RCM) has been utilized for the synthesis of the turriane with a

• -unsaturated ketone delivered the compound 169 (64%). Finally, aromatization of compound 169 by using potassium 3-aminopropylamide (KAPA) gave compound 170 (75%) (Scheme 26). Ring-closing metathesis (RCM): In 2003, Tae and Yang [152] have reported an efficient macrocyclization of various alkenyl derivatives

Hybrid macrocycle formation and spiro annulation on cis-syn-cis-tricyclo[6.3.0.0^2,6]undeca-3,11-dione and its congeners via ring-closing metathesis

• Sambasivarao Kotha,
• Ajay Kumar Chinnam and
• Rashid Ali

Beilstein J. Org. Chem. 2015, 11, 1123–1128, doi:10.3762/bjoc.11.126

• based macrocycle 6 involving Fischer indolization and ring-closing metathesis (RCM). Various spiro-polyquinane derivatives have been assembled via RCM as a key step. Keywords: aza-polyquiananes; Fischer indolization; macrocycles; ring-closing metathesis; spiropolyquinanes; Introduction Design and

• new strategy based on Fischer indolization and ring-closing metathesis as the key steps. To develop a simple synthetic methodology to aza-polycycles and spiropolycycles from readily available starting materials [47][48][49][50][51][52], bicyclic, tricyclic and pentacyclic diones (1–3) were identified

• ]. Also, based on Fischer indolization and ring-closing metathesis (RCM), we have developed a new strategy to indole-based propellane derivatives [57]. Here, the tricyclic dione 2 required was prepared starting with the Cookson’s dione 4 in two steps involving flash vacuum pyrolysis (FVP) and

Further exploration of the heterocyclic diversity accessible from the allylation chemistry of indigo

• Alireza Shakoori,
• John B. Bremner,
• Mohammed K. Abdel-Hamid,
• Anthony C. Willis,
• Rachada Haritakun and
• Paul A. Keller

Beilstein J. Org. Chem. 2015, 11, 481–492, doi:10.3762/bjoc.11.54

• structural complexity through post-allylation ring-closing metathesis, plus new biological activity investigations, which are now reported herein. Results and Discussion A range of strategies are available to potentially control reaction-path selectivity in cascade pathways [5][6] but in these indigo

• 12, with its pendant allyl substituents, affords an ideal substrate for a ring-closing metathesis reaction. In the event, treatment of 12 with Grubbs' II catalyst at reflux in CH2Cl2 produced not the expected 9-membered ring, but rather the novel fused heterocycle 31 in 70% isolated yield (Scheme 10

• ). The structure, including relative stereochemistry, was confirmed by X-ray crystallographic analysis. This compound was formed presumably after initial 9-membered ring production to give 30 in a typical ring-closing metathesis reaction, followed by an intramolecular Claisen rearrangement. Attempts to

Enantioselective synthesis of polyhydroxyindolizidinone and quinolizidinone derivatives from a common precursor

• Nemai Saha and
• Shital K. Chattopadhyay

Beilstein J. Org. Chem. 2014, 10, 3104–3110, doi:10.3762/bjoc.10.327

• from a common intermediate which featured a highly selective dihydroxylation reaction and a RCM reaction as key steps. Keywords: chiral pool; dihydroxylation; indolizidines; quinolizidine; ring-closing metathesis; Introduction Polyhydroxylated indolizidine derivatives have attracted continued

The Shono-type electroorganic oxidation of unfunctionalised amides. Carbon–carbon bond formation via electrogenerated N-acyliminium ions

• Alan M. Jones and
• Craig E. Banks

Beilstein J. Org. Chem. 2014, 10, 3056–3072, doi:10.3762/bjoc.10.323

• ) [76][77]. The ability to introduce two carbon–carbon bonds on to the same α-carbon to prepare spirocyclic systems is a challenge, yet the application of electrochemistry in tandem with ring closing metathesis (RCM) readily achieved this feat. The use of the Shono-type electrooxidation in natural

Design and synthesis of novel bis-annulated caged polycycles via ring-closing metathesis: pushpakenediol

• Sambasivarao Kotha and
• Mirtunjay Kumar Dipak

Beilstein J. Org. Chem. 2014, 10, 2664–2670, doi:10.3762/bjoc.10.280

• rearrangement, a ring-closing metathesis (RCM) and an alkenyl Grignard addition. The introduction of olefinic moieties in the pentacycloundecane (PCUD) framework at appropriate positions followed by RCM led to the formation of novel heptacyclic cage systems. Keywords: Diels–Alder cycloaddition; Grignard

• addition; pentacycloundecane (PCUD); ring-closing metathesis; Introduction Caged polycyclic compounds draw the attention of synthetic organic chemists due to their unusual reactivity patterns as well as their strained nature [1][2][3][4][5][6][7][8][9]. Several pentacycloundecane (PCUD) related molecules

• . The addition of alkyl groups can take place from the less hindered exo side of this caged system. If the R and R’ groups contain unsaturated systems one can think of constructing additional rings on the pentacyclic framework by utilizing ring-closing metathesis (RCM). By varying the length of

Formal total syntheses of classic natural product target molecules via palladium-catalyzed enantioselective alkylation

• Yiyang Liu,
• Marc Liniger,
• Ryan M. McFadden,
• Jenny L. Roizen,
• Jacquie Malette,
• Corey M. Reeves,
• Douglas C. Behenna,
• Masaki Seto,
• Jimin Kim,
• Justin T. Mohr,
• Scott C. Virgil and
• Brian M. Stoltz

Beilstein J. Org. Chem. 2014, 10, 2501–2512, doi:10.3762/bjoc.10.261

• could be transformed into cycloalkenes with a stereocenter remote to the olefin [44], chiral diene 27 was submitted to ring closing metathesis to generate 28 in 90% yield and 92% ee [43]. Cyclohexene 28 readily undergoes acetonide cleavage and periodic acid oxidation to provide carboxylic acid (S)-22

A modular phosphate tether-mediated divergent strategy to complex polyols

• Paul R. Hanson,
• Susanthi Jayasinghe,
• Soma Maitra,
• Cornelius N. Ndi and
• Rambabu Chegondi

Beilstein J. Org. Chem. 2014, 10, 2332–2337, doi:10.3762/bjoc.10.242

• generates five polyol fragments, bearing differential Z- and E-olefins, from a pair of olefinic-alcohol components A and B and a pseudo-C2-symmetric phosphoryl chloride (S,S)-1. Moreover, the method relies on simple "order of addition" of components for the phosphoryl coupling, ring-closing metathesis (RCM

De novo macrolide–glycolipid macrolactone hybrids: Synthesis, structure and antibiotic activity of carbohydrate-fused macrocycles

• Richard T. Desmond,
• Anniefer N. Magpusao,
• Chris Lorenc,
• Jeremy B. Alverson,
• Nigel Priestley and
• Mark W. Peczuh

Beilstein J. Org. Chem. 2014, 10, 2215–2221, doi:10.3762/bjoc.10.229

• . Results and Discussion The syntheses of 5 and 6 (Scheme 1) generally followed a ring closing metathesis (RCM) strategy that had been established previously [9]. C4,C6-O-Benzylidene-protected allyl glucoside 7, as a mixture of α- and β-anomers, was the starting material for the synthesis. In the first step

• 5 and 6 from an angle perpendicular to the D-glucose plane; e) and f) Newman projections, sighting down the glycosidic bond, of 5 and 6. Synthesis of macrolides 5 and 6 by a ring closing metathesis strategy. Selected bond angles for 5 and 6 from X-ray crystallographic data. MIC (μg/mL) values for

Relay cross metathesis reactions of vinylphosphonates

• Raj K. Malla,
• Jeremy N. Ridenour and
• Christopher D. Spilling

Beilstein J. Org. Chem. 2014, 10, 1933–1941, doi:10.3762/bjoc.10.201

• metathesis reactions (Scheme 3), this approach to the synthesis of cetrolobine appeared to have little merit. However, Hoye et al. reported the concept of “relay ring closing metathesis (RRCM)”, wherein typically unreactive α,ω-dienes bearing 1,1-disubstituted ethylene moieties 9 would react via the

• intermediacy of an additional terminal alkene 11 (Scheme 3) [19][20][21]. Similarly, Hansen and Lee employed an allyl ether to activate enynes toward cross metathesis [22]. Furthermore, there are several examples of vinylphosphonates participating in ring closing metathesis (RCM) reactions [23][24][25

• of vinylphosphonate 21a with styrenes. The dimeric product 27 was not observed during the cross metathesis of the vinylphosphonate 21a with methyl acrylate. Diallyl vinylphosphonates (28) are reported to undergo ring closing metathesis to give either 7-membered (29) or 5-membered (30) phosphorus

Application of cyclic phosphonamide reagents in the total synthesis of natural products and biologically active molecules

• Thilo Focken and
• Stephen Hanessian

Beilstein J. Org. Chem. 2014, 10, 1848–1877, doi:10.3762/bjoc.10.195

Olefin cross metathesis based de novo synthesis of a partially protected L-amicetose and a fully protected L-cinerulose derivative

• Bernd Schmidt and
• Sylvia Hauke

Beilstein J. Org. Chem. 2014, 10, 1023–1031, doi:10.3762/bjoc.10.102

• or its epimer rhodinose, respectively [33]. An approach to amicetose (and a few other 6-desoxy sugars) involves the formation of an enantiopure β,γ-unsaturated δ-valerolactone via ring closing metathesis (RCM). The RCM product is subsequently converted into L-amicetose in four steps [34

Phosphinate-containing heterocycles: A mini-review

• Olivier Berger and
• Jean-Luc Montchamp

Beilstein J. Org. Chem. 2014, 10, 732–740, doi:10.3762/bjoc.10.67

• phosphinic acid using different alcohols in large excess (Scheme 1) [11][12]. Six phospholes 2a–f were prepared in yields up to 94%. Montchamp and coworkers have synthesized phospholes 4a,b by ring closing metathesis using 2 or 5 mol % of 2nd generation Grubbs’ catalyst (Scheme 2) [13][14]. Two compounds 4a

• corresponding analog of cyclic AMP, but no biological activity was reported. 1,2-Oxaphosphorines Gouverneur and coworkers have realized the synthesis of several 1,2-oxaphosphorine derivatives 53a–k using diastereoselective ring closing metathesis with 2 to 4 mol % of various catalysts (Scheme 22) [34]. During

• and broader structural diversity. While, like with any other P-heterocycles the phosphinates can be employed for the synthesis of novel phosphine ligands, their potential for the discovery of novel biologically active motifs is tantalizing. McCormack synthesis. Ring-closing metathesis. Phospha