Synthesis of heterocycles based on azomethine ylides from α-amino acids (or amines) and carbonyl compounds

• Ekaterina V. Berezhnaya,
• Alexander I. Ponyaev,
• Vitali M. Boitsov and
• Alexander V. Stepakov

Beilstein J. Org. Chem. 2026, 22, 705–741, doi:10.3762/bjoc.22.55

• derivatives with multiple chiral centers under high regio- and stereocontrol. Currently, strategies using azomethine ylides based on imino esters or α-amino acids with a variety of cyclic and acyclic carbonyl compounds dominate. Enantioselective (3 + 2) cycloaddition reactions of azomethine ylides obtained

• with a dipolarophile, such as an alkene or alkyne, to form a five-membered heterocycle in one step. Currently, this type of reaction allows for the efficient preparation of bi- and polycyclic fused or spiro-linked structures with multiple chiral centers and high regio- and stereocontrol [1][2][3][4

Total syntheses of highly oxidative Ryania diterpenoids facilitated by innovations in synthetic strategies

• Zhi-Qi Cao,
• Jin-Bao Qiao and
• Yu-Ming Zhao

Beilstein J. Org. Chem. 2025, 21, 2553–2570, doi:10.3762/bjoc.21.198

• of the non-naturally produced ryanodol (4) and its dehydrated derivative, anhydroryanodol (10) [30] (Scheme 2). Given the highly complex fused-ring system and the stereochemical challenges posed by multiple chiral centers, the author utilized the Diels–Alder reaction, a prominent representative of

• reaction – a powerful method for building five-membered rings. This single [2 + 2 + 1] cycloaddition step efficiently converted a simple linear precursor into a complex bicyclic system. Subsequent late-stage modifications of the enone skeleton introduced multiple chiral centers, significantly enhancing

The application of desymmetric enantioselective reduction of cyclic 1,3-dicarbonyl compounds in the total synthesis of terpenoid and alkaloid natural products

• Dong-Xing Tan and
• Fu-She Han

Beilstein J. Org. Chem. 2025, 21, 2085–2102, doi:10.3762/bjoc.21.164

• cyclic 1,3-dicarbonyl compounds has invigorated the field of terpenoid and alkaloid natural products synthesis because of its multiple advantages. Specifically, such strategy allows for an efficient construction of multiple chiral centers by employing easily accessible or commercially available symmetric

Enantioselective desymmetrization strategy of prochiral 1,3-diols in natural product synthesis

• Lihua Wei,
• Rui Yang,
• Zhifeng Shi and
• Zhiqiang Ma

Beilstein J. Org. Chem. 2025, 21, 1932–1963, doi:10.3762/bjoc.21.151

• group such as a chiral sulfinyl group is effective in local desymmetrization, while substrates bearing caged frameworks and multiple chiral centers can also realize the desymmetrization. The Cook group reported the first total synthesis of (−)-vincamajinine and (−)-11-methoxy-17-epivincamajine

Construction of highly enantioenriched spirocyclopentaneoxindoles containing four consecutive stereocenters via thiourea-catalyzed asymmetric Michael–Henry cascade reactions

• Yonglei Du,
• Jian Li,
• Kerong Chen,
• Chenglin Wu,
• Yu Zhou and
• Hong Liu

Beilstein J. Org. Chem. 2017, 13, 1342–1349, doi:10.3762/bjoc.13.131

• stereocenters and a unique quaternary stereogenic center, with good yields, and excellent diastereoselectivity and enantioselectivity using thiourea-catalyzed Michael–Henry cascade reactions. We anticipate that this reaction will simplify the synthesis of complex spirooxindoles containing multiple chiral

• centers with potential pharmacological properties. Experimental General procedure for the synthesis of products (3a–j): To a mixture of 1a–j (0.11 mmol) and 2a (0.1 mmol) in CH2Cl2 (3 mL) was added catalyst d (0.01 mmol). Then the mixture was stirred at −20 °C for 12 h. After completion of the reaction

cis-Diastereoselective synthesis of chroman-fused tetralins as B-ring-modified analogues of brazilin

• Dimpee Gogoi,
• Runjun Devi,
• Pallab Pahari,
• Bipul Sarma and
• Sajal Kumar Das

Beilstein J. Org. Chem. 2016, 12, 2816–2822, doi:10.3762/bjoc.12.280

• of two or more privileged scaffolds leads to geometrically well-defined rigid polycyclic structures with enhanced receptor-binding selectivity. Thus, the design and synthesis of structurally diverse, privileged structure-based polycyclic molecules with multiple chiral centers has been intensely

Stereoselective amine-thiourea-catalysed sulfa-Michael/nitroaldol cascade approach to 3,4,5-substituted tetrahydrothiophenes bearing a quaternary stereocenter

• Sara Meninno,
• Chiara Volpe,
• Giorgio Della Sala,
• Amedeo Capobianco and
• Alessandra Lattanzi

Beilstein J. Org. Chem. 2016, 12, 643–647, doi:10.3762/bjoc.12.63

• bearing multiple chiral centers increased over the last years [1]. Indeed, chiral non-racemic functionalized tetrahydrothiophenes are endowed with different biological activities [2][3][4][5] and they are useful ligands in asymmetric catalysis [6]. However, few asymmetric approaches are available to

(Thio)urea-mediated synthesis of functionalized six-membered rings with multiple chiral centers

• Giorgos Koutoulogenis,
• Nikolaos Kaplaneris and
• Christoforos G. Kokotos

Beilstein J. Org. Chem. 2016, 12, 462–495, doi:10.3762/bjoc.12.48

• main tools a synthetic chemist has to perform asymmetric catalysis. In this review the synthesis of six-membered rings, that contain multiple chiral centers, either by a ring closing process or by a functionalization reaction on an already existing six-membered ring, utilizing bifunctional (thio)ureas

• products, pharmaceuticals and agrochemicals, thus, a lot of effort has been put by the synthetic community to provide mild, reliable, robust and operationally simple methods to construct them. Of the vast variety of six-membered rings, those with multiple chiral centers pose the most difficult synthetic

• challenge, because not only the regiochemical outcome, but also the stereochemical outcome of the reaction must be carefully controlled. Since its rebirth, organocatalysis has made many contributions in the synthesis of six-membered rings with multiple chiral centers, this area has been reviewed in the past

Synthesis and self-assembly of 1-deoxyglucose derivatives as low molecular weight organogelators

• Guijun Wang,
• Hao Yang,
• Sherwin Cheuk and
• Sherman Coleman

Beilstein J. Org. Chem. 2011, 7, 234–242, doi:10.3762/bjoc.7.31

• because they are naturally abundant and possess multiple chiral centers that can be selectively functionalized [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37]. Sugar-based supramolecular hydrogels are being explored as biocompatible soft materials and as