Dioxazolones as electrophilic amide sources in copper-catalyzed and -mediated transformations

• Seungmin Lee,
• Minsuk Kim,
• Hyewon Han and
• Jongwoo Son

Beilstein J. Org. Chem. 2025, 21, 200–216, doi:10.3762/bjoc.21.12

• -phosphorylation of dioxazolones using organic phosphines and copper catalysts [91]. As shown in Scheme 6, a variety of dioxazolones 14 were explored for the synthesis of N-acyl iminophosphoranes 16. Dioxazolones containing aryl and heteroaryl groups were successfully transformed into the desired products in high

• yields (16a–c). Moreover, alkyl groups were tolerated during the formation of N-acyl iminophosphoranes (16d, 16f). It is noteworthy that dioxazolones derived from bioactive motifs, such as peptides, natural products, and commercially available drugs were also compatible with this transformation

• the copper-catalyzed synthesis of N-acyl iminophosphoranes from dioxazolones. Proposed reaction mechanism for the copper-catalyzed S-amidation of thiols. Proposed reaction mechanism for the copper-catalyzed hydroamidation of vinylarenes. Proposed reaction mechanism for the copper-catalyzed amidation

New efficient synthesis of polysubstituted 3,4-dihydroquinazolines and 4H-3,1-benzothiazines through a Passerini/Staudinger/aza-Wittig/addition/nucleophilic substitution sequence

• Long Zhao,
• Mao-Lin Yang,
• Min Liu and
• Ming-Wu Ding

Beilstein J. Org. Chem. 2022, 18, 286–292, doi:10.3762/bjoc.18.32

• obtained (compounds 8s, NR4R5 = NPh2). The aza-Wittig reaction of iminophosphoranes 5 with an excess of CS2 took place smoothly at 40 °C to produce isothiocyanates 9, which were allowed to react with secondary amines to generate thiourea intermediates 10. In the presence of K2CO3 in CH3CN at refluxing

Total synthesis of pyrrolo[2,3-c]quinoline alkaloid: trigonoine B

• Takashi Nishiyama,
• Erina Hamada,
• Daishi Ishii,
• Yuuto Kihara,
• Nanase Choshi,
• Natsumi Nakanishi,
• Mari Murakami,
• Kimiko Taninaka,
• Noriyuki Hatae and
• Tominari Choshi

Beilstein J. Org. Chem. 2021, 17, 730–736, doi:10.3762/bjoc.17.62

• . Consequently, we decided to develop a new synthetic strategy for the preparation of trigonoine B (1). Carbodiimides are valuable synthetic intermediates that can be obtained by an aza-Wittig reaction of isocyanates with iminophosphoranes or by dehydration of urea [26]. Molina et al. previously reported the

• synthesis of 2-aminopyridine derivatives through an electrocyclization of conjugated carbodiimides derived from an aza-Wittig reaction of iminophosphoranes and isocyanates [27]. Hibino and co-workers also achieved the preparation of mutagenic amino-α-carbolines (2-amino-9H-pyrido[2,3-b]indole, AαC) and

• MeAαC by the electrocyclization of 3-alkenyl-2-carbodiimidoindole derivatives obtained by an aza-Wittig reaction of indol-2-yl-iminophosphoranes and isocyanates [28]. In this work, we report the first total synthesis of trigonoine B (1) involving the construction of a pyrrolo[2,3-c]quinoline framework

Phosphazene-catalyzed desymmetrization of cyclohexadienones by dithiane addition

• Matthew A. Horwitz,
• Elisabetta Massolo and
• Jeffrey S. Johnson

Beilstein J. Org. Chem. 2017, 13, 762–767, doi:10.3762/bjoc.13.75

• ; desymmetrization; dithiane; iminophosphoranes; organocatalysis; phosphazenes; Findings Desymmetrization has become a well-developed strategy for the construction of complex molecular frameworks [1][2][3][4][5][6]. Cyclohexadienones are multipurpose synthetic building blocks that have found a central role in

• cyclohexadienone (1g), the reaction proved to be completely regioselective, only allowing conjugate addition to the less substituted position. We attempted to render the reaction enantioselective using chiral iminophosphoranes (Figure 1) structurally related to P2-t-Bu phosphazene, which are known to be

Catalytic Wittig and aza-Wittig reactions

• Zhiqi Lao and
• Patrick H. Toy

Beilstein J. Org. Chem. 2016, 12, 2577–2587, doi:10.3762/bjoc.12.253

• with 44 produced cyclized final products 54 via iminophosphoranes 60. Phosphine-catalyzed reactions The initial research in this area was performed by Floris L. van Delft and co-workers who reported the synthesis of 61 and its use in catalytic Staudinger reactions for the reduction of azides 62 to

• via intermediate iminophosphoranes 70, using the combination of titanium tetraisopropoxide and tetramethyldisiloxane (TMDS) for the in situ reduction of byproduct 2 (Scheme 18) [36]. This group has more recently studied catalytic aza-Wittig reactions using carboxylic acid anhydrides as the starting

One-pot sequential synthesis of isocyanates and urea derivatives via a microwave-assisted Staudinger–aza-Wittig reaction

• Diego Carnaroglio,
• Katia Martina,
• Giovanni Palmisano,
• Andrea Penoni,
• Claudia Domini and
• Giancarlo Cravotto

Beilstein J. Org. Chem. 2013, 9, 2378–2386, doi:10.3762/bjoc.9.274

• by carbon dioxide (CO2), which is nontoxic, abundant, and economical, is the main advantage of this reaction. The mechanism of this transformation passes through iminophosphoranes that are versatile intermediates and can react with CO2 to generate isocyanates [20]. This reaction is compatible with a

A facile synthesis and fungicidal activities of 2-(alkylamino)-5,6-dimethylthieno[2,3-d]pyrimidin- 4(3H)-ones

• Yang-Gen Hu,
• Ai-Hua Zheng,
• Xu-Zhi Ruan and
• Ming-Wu Ding

Beilstein J. Org. Chem. 2008, 4, No. 49, doi:10.3762/bjoc.4.49

• activities against six kinds of fungi. Keywords: 2-(alkylamino)-5,6-dimethylthieno[2,3-d]pyrimidin-4(3H)-one; aza-Wittig reaction; fungicidal activity; synthesis; Introduction Over the past ten years, aza-Wittig reactions of functionalized iminophosphoranes with isocyanates have been applied to produce

• interested in the synthesis of a series of new heterocyclic compounds via aza-Wittig reaction of α- or β-(ethoxycarbonyl)-substituted iminophosphoranes with aromatic isocyanates and subsequent reaction with various nucleophiles under mild conditions [11][12][13][14]. Herein we wish to report an efficient

Synthesis of coumarin or ferrocene labeled nucleosides via Staudinger ligation

• Ivana Kosiova,
• Andrea Janicova and
• Pavol Kois

Beilstein J. Org. Chem. 2006, 2, No. 23, doi:10.1186/1860-5397-2-23

• gives iminophosphoranes which can react with almost any kind of electrophilic reagent, e.g. aldehydes/ketones to form imines or esters to form amides. This so-called Staudinger ligation has been employed in a wide range of applications as a general tool for bioconjugation including specific labeling of

• , boranes) and at N3 with nucleophiles, very frequently with phosphorous nucleophiles. Reaction of azides with triaryl phosphines under mild conditions gives iminophosphoranes without formation of any byproducts. [14] The intermediate which is formed almost quantitatively can be rapidly hydrolysed to the

• primary amine and triarylphosphine oxide. This Staudinger reduction is a frequently used method for the smooth reduction of azides to amines. Iminophosphoranes can react with almost any kind of electrophilic reagent, [15][16] e.g. aldehydes or ketones to form imines. Also less reactive carbonyl