Chiral isothiourea-catalyzed kinetic resolution of 4-hydroxy[2.2]paracyclophane

• David Weinzierl and
• Mario Waser

Beilstein J. Org. Chem. 2021, 17, 800–804, doi:10.3762/bjoc.17.68

• transformation into diastereomers by esterification with chiral acid chlorides [19][20] as well as the kinetic resolution (KR) of racemic esters of 2 via an enzymatic hydrolysis [25][26][27] were very successfully used to access enantioenriched 2. Recently, Akiyama and co-workers reported the kinetic resolution

• of rac-PHANOL (4,12-dihydroxy[2.2]paracyclophane) by means of a chiral phosphoric acid-catalyzed esterification with achiral anhydrides [28]. This method allowed for high s-factors but was unfortunately not satisfyingly applicable to rac-4-hydroxy[2.2]paracyclophane (rac-2) [28]. Considering the

• interest in compound 2, we thus thought about developing an alternative organocatalytic kinetic resolution protocol to control the esterification of rac-2. Chiral isothioureas (ITUs) emerged as easily available and powerful catalysts for numerous applications [29][30][31][32] and have been very

[2 + 1] Cycloaddition reactions of fullerene C₆₀ based on diazo compounds

• Yuliya N. Biglova

Beilstein J. Org. Chem. 2021, 17, 630–670, doi:10.3762/bjoc.17.55

• methanofullerene-appended dicarboxylic acid 85 synthesized from 10 is a versatile synthon for conversion into numerous derivatives (Scheme 25). The reactivity of compound 85 was studied under DCC-promoted esterification conditions (see adducts 8 and 86) and amidation conditions (see adducts 21 and 22). Hummelen

Menthyl esterification allows chiral resolution for the synthesis of artificial glutamate analogs

• Kenji Morokuma,
• Shuntaro Tsukamoto,
• Kyosuke Mori,
• Kei Miyako,
• Ryuichi Sakai,
• Raku Irie and
• Masato Oikawa

Beilstein J. Org. Chem. 2021, 17, 540–550, doi:10.3762/bjoc.17.48

• enantiospecific synthesis of two artificial glutamate analogs designed based on IKM-159, an antagonist selective to the AMPA-type ionotropic glutamate receptor. The synthesis features the chiral resolution of the carboxylic acid intermediate by the esterification with ʟ-menthol, followed by a configurational

• ], the heterotricyclic framework was constructed over a five-step sequence including the domino metathesis reaction as a key step to give (rac)-7. The subsequent three steps from (rac)-7 (esterification with CH2N2, PMB removal, and ester hydrolysis) had been proven to be promising for the preparation of

• be effective here (Scheme 2). Thus, the esterification mediated by 2-methyl-6-nitrobenzoic anhydride (MNBA, Shiina esterification) [9], followed by chromatographic separation of the diastereomers, successfully generated the (2S)-isomer 9* (tR 7.0 min) and the (2R)-isomer 9 (tR 11.5 min) in 45.3% and

Synthetic strategies of phosphonodepsipeptides

• Jiaxi Xu

Beilstein J. Org. Chem. 2021, 17, 461–484, doi:10.3762/bjoc.17.41

• reacted with benzyl (R)-lactate ((R)-26b) or benzyl (R)-2-phenyllactate ((R)-26f). The optically active phosphonodepsidipeptides 28 were obtained after hydrogenolysis and tested for their biological activity (Scheme 5) [22]. The phosphonodepsidipeptides 31 were synthesized by the esterification of N-Cbz

• tryptophan amide with 4-nitrobenzyl (R)-N-Fmoc 1-amino(cyclohexyl)methylphosphonochloridate (38), which was prepared from diethyl (R)-N-Fmoc 1-amino(cyclohexyl)methylphosphonate (36) via a selective basic hydrolysis, chlorination, esterification with 4-nitrobenzyl alcohol, selective basic hydrolysis, and

• nucleophilic esterification of potassium 1-(N-benzyloxycarbonylamino)alkylphosphonates 172 with alkyl halides in the presence of 18-crown-6. They also prepared a phosphonodepsidipeptide 174 with ethyl chloroacetate (173) as an electrophile (Scheme 33) [53]. The macrocyclic peptidyl phosphonodepsipeptide 180

Coupling biocatalysis with high-energy flow reactions for the synthesis of carbamates and β-amino acid derivatives

• Alexander Leslie,
• Thomas S. Moody,
• Megan Smyth,
• Scott Wharry and
• Marcus Baumann

Beilstein J. Org. Chem. 2021, 17, 379–384, doi:10.3762/bjoc.17.33

• utilized as it is frequently used for esterification reactions [26][27][28]. CALB could convert benzyl alcohol in the presence of vinyl butyrate into benzyl butyrate and acetaldehyde. To demonstrate the feasibility, the flow process was adapted by mixing a stream of vinyl butyrate (4, 3 equiv in toluene

Regioselective chemoenzymatic syntheses of ferulate conjugates as chromogenic substrates for feruloyl esterases

• Olga Gherbovet,
• Fernando Ferreira,
• Apolline Clément,
• Mélanie Ragon,
• Julien Durand,
• Sophie Bozonnet,
• Michael J. O'Donohue and
• Régis Fauré

Beilstein J. Org. Chem. 2021, 17, 325–333, doi:10.3762/bjoc.17.30

• the primary hydroxy group compare favorably with the previously reported overall yield (46 and 47%, respectively, in three steps) [15][16][17][29], which relate to the selective enzymatic O-5-deacetylation and esterification of the primary hydroxy group and a final deprotection of the 2,3-O-acetyl

The preparation and properties of 1,1-difluorocyclopropane derivatives

• Kymbat S. Adekenova,
• Peter B. Wyatt and
• Sergazy M. Adekenov

Beilstein J. Org. Chem. 2021, 17, 245–272, doi:10.3762/bjoc.17.25

• hydrogenation of difluorocyclopropenes [73][79]. Enzymatic hydrolysis or esterification: The first example of the enzymatic resolution of gem-difluorocyclopropanes was reported by Itoh et al. [80]. The prochiral diacetate of cis-1,2-bis-(hydroxymethyl)-3,3-difluorocyclopropane was converted into the

Insight into functionalized-macrocycles-guided supramolecular photocatalysis

• Minzan Zuo,
• Krishnasamy Velmurugan,
• Kaiya Wang,
• Xueqi Tian and
• Xiao-Yu Hu

Beilstein J. Org. Chem. 2021, 17, 139–155, doi:10.3762/bjoc.17.15

• macrocycle has inherent chromophores that can function as photosensitizers, the efficiency of the energy transfer will be higher and the systems will be simplified. 3) Other kinds of macrocycle-based catalysis need to be explored, such as esterification, polymerization, redox reaction, etc. 4) Hyperbranched

Supramolecular polymerization of sulfated dendritic peptide amphiphiles into multivalent L-selectin binders

• David Straßburger,
• Svenja Herziger,
• Katharina Huth,
• Moritz Urschbach,
• Rainer Haag and
• Pol Besenius

Beilstein J. Org. Chem. 2021, 17, 97–104, doi:10.3762/bjoc.17.10

• intact. Commonly this heterofunctionalization is achieved using esterification of trimesic acid and subsequent partial hydrolysis, however, this route suffers from difficult purification steps [37][38]. Here, it was conveniently achieved in one step via a solid-phase supported approach, using trimesic

Chemical constituents of Chaenomeles sinensis twigs and their biological activity

• Joon Min Cha,
• Dong Hyun Kim,
• Lalita Subedi,
• Zahra Khan,
• Sang Un Choi,
• Sun Yeou Kim and
• Chung Sub Kim

Beilstein J. Org. Chem. 2020, 16, 3078–3085, doi:10.3762/bjoc.16.257

• obtained by geometry optimization at the MMFF force field. (C) ECD spectrum of 1 and structures of 1 (6S) and 13 (6R). (D) Enzymatic hydrolysis of 1 followed by modified Mosher’s esterification of the aglycone 1a. 1H [ppm, mult., (J in Hz)] and 13C NMR data of compounds 1 and 1a in methanol-d4

Easy access to a carbohydrate-based template for stimuli-responsive surfactants

• Thomas Holmstrøm,
• Daniel Raydan and
• Christian Marcus Pedersen

Beilstein J. Org. Chem. 2020, 16, 2788–2794, doi:10.3762/bjoc.16.229

• with high regioselectivity via the Černý epoxide [20]. Results and Discussion Synthesis The synthesis was initiated by a regioselective esterification of levoglucosan (1) with tosyl chloride in pyridine, first presented by Černý and co-workers, in order to afford the 1,6-anhydro-2,4-di-O-tosyl-β-ᴅ

Hierarchically assembled helicates as reaction platform – from stoichiometric Diels–Alder reactions to enamine catalysis

• David Van Craen,
• Jenny Begall,
• Johannes Großkurth,
• Leonard Himmel,
• Oliver Linnenberg,
• Elisabeth Isaak and
• Markus Albrecht

Beilstein J. Org. Chem. 2020, 16, 2338–2345, doi:10.3762/bjoc.16.195

• the amino alcohols 10a–d were protected with a Boc group [42][43]. Esterification of the protected alcohols 11a–d [33][44] with 2,3-dioxosulfinylbenzoyl chloride obtained from 2,3-dihydroxybenzoic acid and thionyl chloride afforded the N-Boc-substituted catechol ligands 12a–d [33][36]. They were

Synthetic approaches to bowl-shaped π-conjugated sumanene and its congeners

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 2212–2259, doi:10.3762/bjoc.16.186

• common organic solvents, they first tried the esterification reaction with soluble monoiodosumanene 79 using Pd(OAc)2 under CO atmosphere and obtained the desired sumanene methyl ester in very low yield. Surprisingly, when they used hexabromosumanene 94 under similar reaction conditions, no product

• formation was observed. Therefore, they used a Pd-catalyzed carbonylative esterification in the presence of phenyl formate which in situ generated CO and phenol to provide the required product 97 in 73% yield (Scheme 24). In an independent work reported in 2017, Fukushima and co-workers detailed the

Azo-dimethylaminopyridine-functionalized Ni(II)-porphyrin as a photoswitchable nucleophilic catalyst

• Jannis Ludwig,
• Julian Helberg,
• Hendrik Zipse and
• Rainer Herges

Beilstein J. Org. Chem. 2020, 16, 2119–2126, doi:10.3762/bjoc.16.179

• study is 4-(N,N-dimethylamino)pyridine derivative 1 (Figure 1). The parent 4-(N,N-dimethylamino)pyridine (DMAP, 2) is known as a nucleophilic catalyst in a number of reactions, for example the Baylis–Hillman reaction [27] and the Steglich esterification [28][29]. To achieve control of the catalytic

Muyocopronones A and B: azaphilones from the endophytic fungus Muyocopron laterale

• Ken-ichi Nakashima,
• Junko Tomida,
• Tomoe Tsuboi,
• Yoshiaki Kawamura and
• Makoto Inoue

Beilstein J. Org. Chem. 2020, 16, 2100–2107, doi:10.3762/bjoc.16.177

• MTPA chloride, enolization and esterification at the C-15 position occurred preferentially over the C-3′ position. Therefore, 2.7 equivalents of the (R)- and (S)-MTPA chlorides were used to prepare the (S)- and (R)-MTPA diesters 1a and 1b, respectively (Scheme 1A). Based on the differences in chemical

Synthesis, antiinflammatory activity, and molecular docking studies of bisphosphonic esters as potential MMP-8 and MMP-9 inhibitors

• Abimelek Cortes-Pacheco,
• María Adelina Jiménez-Arellanes,
• Francisco José Palacios-Can,
• José Antonio Valcarcel-Gamiño,
• Rodrigo Said Razo-Hernández,
• María del Carmen Juárez-Vázquez,
• Adolfo López-Torres and
• Oscar Abelardo Ramírez-Marroquín

Beilstein J. Org. Chem. 2020, 16, 1277–1287, doi:10.3762/bjoc.16.108

• [23]. Then, the above-named derivatives were synthesized in a first stage by the esterification of bromoacetyl bromide and the corresponding alcohol. The reaction of ethyl or tert-butyl alcohol and bromoacetyl bromide in the presence of triethylamine in CH2Cl2 yielded the bromoaceto esters 7 and 8 in

Fluorinated phenylalanines: synthesis and pharmaceutical applications

• Laila F. Awad and
• Mohammed Salah Ayoup

Beilstein J. Org. Chem. 2020, 16, 1022–1050, doi:10.3762/bjoc.16.91

• affecting the newly introduced fluorine atom was attempted by a two-step, one-pot protocol involving an in situ esterification of a highly electrophilic pyridinium triflate intermediate [77] and afforded the anti-β-fluoro-α-amino acid methyl ester 160a in 52% yield and with 98.8% ee (Scheme 39). On the

Efficient synthesis of piperazinyl amides of 18β-glycyrrhetinic acid

• Dong Cai,
• ZhiHua Zhang,
• Yufan Meng,
• KaiLi Zhu,
• LiYi Chen,
• ChangXiang Yu,
• ChangWei Yu,
• ZiYi Fu,
• DianShen Yang and
• YiXia Gong

Beilstein J. Org. Chem. 2020, 16, 798–808, doi:10.3762/bjoc.16.73

• compound 8 involves the amidation of 18β-glycyrrhetinic acid followed by the esterification with acetic anhydride. Finally, compound 8 underwent N-Boc deprotection to prepare product 4. To ascertain the scope of the reaction, another C-3 ester derivative 17 was tested under the optimized reaction

• yield. The reaction was completed in 30 min. The principal advantages of this method are that there is no solvent required, and that the reaction time is shorter than in previous cases [16], since the acid formed during the reaction may catalyze the esterification reaction of 18β-glycyrrhetinic acid

Design and synthesis of diazine-based panobinostat analogues for HDAC8 inhibition

• Sivaraman Balasubramaniam,
• Sajith Vijayan,
• Liam V. Goldman,
• Xavier A. May,
• Kyra Dodson,
• Sweta Adhikari,
• Fatima Rivas,
• Davita L. Watkins and
• Shana V. Stoddard

Beilstein J. Org. Chem. 2020, 16, 628–637, doi:10.3762/bjoc.16.59

• esterification reaction using methanol mediated by sulfuric acid under heating conditions to provide the compound in 81% yield. The methyl ester 5 was reduced to aldehyde 6 using DIBAL-H at −78 °C. While TLC analysis revealed complete conversion of the ester to aldehyde, the isolated yield was poor (20%). The

Oligomeric ricinoleic acid preparation promoted by an efficient and recoverable Brønsted acidic ionic liquid

• Fei You,
• Xing He,
• Song Gao,
• Hong-Ru Li and
• Liang-Nian He

Beilstein J. Org. Chem. 2020, 16, 351–361, doi:10.3762/bjoc.16.34

• ]. The presence of both hydroxy and carboxy groups in the molecule of ricinoleic acid enables it to undergo intermolecular esterification, thus resulting in the formation of the oligomeric ricinoleic acid. The oligomeric ricinoleic acid with different acid value (which is an indirect index for

• excellent catalytic activity for this intermolecular esterification reaction and Brønsted acidic ionic liquids have been successfully used as catalyst in organic syntheses [29][30][31], we designed a series of Brønsted acidic ionic liquids and applied them as catalysts for the preparation of oligomeric

• depicted in Scheme 1. Results and Discussion Considering protic acids have catalytic effects on the esterification reaction, we designed and synthesized a series of ILs containing protic anions as shown in Scheme 2. With the synthesized ILs as catalyst, the ricinoleic acid esterification was performed and

A green, economical synthesis of β-ketonitriles and trifunctionalized building blocks from esters and lactones

• Daniel P. Pienaar,
• Kamogelo R. Butsi,
• Amanda L. Rousseau and
• Dean Brady

Beilstein J. Org. Chem. 2019, 15, 2930–2935, doi:10.3762/bjoc.15.287

• , atom-economical ring opening of enolizable δ-valerolactone (3, Scheme 1). Although a two-step (or four-step, should hydroxy group O-protection prove to be necessary prior to acylation) protocol could, in theory, be envisaged to produce β-ketonitrile 2 from 3 by ring-opening esterification to afford

A review of asymmetric synthetic organic electrochemistry and electrocatalysis: concepts, applications, recent developments and future directions

• Munmun Ghosh,
• Valmik S. Shinde and
• Magnus Rueping

Beilstein J. Org. Chem. 2019, 15, 2710–2746, doi:10.3762/bjoc.15.264

• ). Constant current electrolysis of 89 in a single compartment cell using a sacrificial Mg anode was conducted in the presence of a Ni catalyst and chiral ligand 90. After esterification and purification, 91 was isolated in a good yield and with moderate enantioselectivity [70]. In another recent report, Guo

Safe and highly efficient adaptation of potentially explosive azide chemistry involved in the synthesis of Tamiflu using continuous-flow technology

• Cloudius R. Sagandira and
• Paul Watts

Beilstein J. Org. Chem. 2019, 15, 2577–2589, doi:10.3762/bjoc.15.251

• continuous-flow technology. The two steps involving azide chemistry in flow are reported herein (Scheme 2), with the vision of further integrating the other steps towards continuous-flow total synthesis of this drug. To this effect, we have already reported continuous flow shikimic acid (3) esterification

Formation of alkyne-bridged ferrocenophanes using ring-closing alkyne metathesis on 1,1’-diacetylenic ferrocenes

• Celine Bittner,
• Dirk Bockfeld and
• Matthias Tamm

Beilstein J. Org. Chem. 2019, 15, 2534–2543, doi:10.3762/bjoc.15.246

• synthesized via an esterification reaction starting from symmetrical 1,1’-ferrocenoyl dichloride (3) [92] as shown in Scheme 1. To a solution of the corresponding 1-alkynol (13.5 mmol), NEt3 (13.5 mmol), and 4-dimethylaminopyridine (DMAP, 0.5 mmol) in dichloromethane (DCM, 20 mL) at 0 °C the dichloride 3 (2 g

• positions of the THF molecules are shown. Selected bond lengths [Å] and angles [°] are given in Supporting Information File 1, Tables S1 and S2. Synthesis of substrates 1 (a n = 2; b n = 3) via esterification of 3 and following RCAM with catalyst MoF6 to ferrocenophanes 2 (a: n = 2; b: n = 3); a) HO(CH2)nC

Mono- and bithiophene-substituted diarylethene photoswitches with emissive open or closed forms

• A. Lennart Schleper,
• Mariano L. Bossi,
• Vladimir N. Belov and
• Stefan W. Hell

Beilstein J. Org. Chem. 2019, 15, 2344–2354, doi:10.3762/bjoc.15.227

• ligands. The reaction with pinacolborane (HB(pin)) gave ester 9 in 97% yield [11]. Another ester (10) was synthesized by bromination of 3-thiopheneacetic acid with NBS (applying an ultrasound bath) followed by esterification of the crude product with methanol in the presence of sulfuric acid [12]. Other