Synthetic strategies for the preparation of γ-phostams: 1,2-azaphospholidine 2-oxides and 1,2-azaphospholine 2-oxides

• Jiaxi Xu

Beilstein J. Org. Chem. 2022, 18, 889–915, doi:10.3762/bjoc.18.90

• 105 via the copper-catalyzed intramolecular carbene aromatic C–H bond insertion (Scheme 20) [44]. This is an efficient synthetic strategy for 3-benzoyl-2-ethoxy-1,3-dihydrobenzo[d][1,2]azaphosphole 2-oxides 106 through the formation of the C–C bond neighboring at the ring phosphorus atom. Synthesis

Iridium-catalyzed hydroacylation reactions of C1-substituted oxabenzonorbornadienes with salicylaldehyde: an experimental and computational study

• Angel Ho,
• Austin Pounder,
• Krish Valluru,
• Leanne D. Chen and
• William Tam

Beilstein J. Org. Chem. 2022, 18, 251–261, doi:10.3762/bjoc.18.30

• regioselectivity. The mechanism and origins of selectivity in the iridium-catalyzed hydroacylation reaction has been examined at the M06/Def2TZVP level of theory. The catalytic cycle consists of three key steps including oxidative addition into the aldehyde C–H bond, insertion of the olefin into the iridium

Ruthenium-based olefin metathesis catalysts with monodentate unsymmetrical NHC ligands

• Veronica Paradiso,
• Chiara Costabile and
• Fabia Grisi

Beilstein J. Org. Chem. 2018, 14, 3122–3149, doi:10.3762/bjoc.14.292

• , Figure 6), developed by Grubbs and co-workers, is based on a chelating NHC ligand that is derived from an intramolecular carboxylate-driven C–H bond insertion of the adamantyl N-substituent of the same NHC ligand in complex 22 [20]. Unsymmetrical complexes bearing smaller N-alkyl groups (Figure 7) were

The synthesis of functionalized bridged polycycles via C–H bond insertion

• Jiun-Le Shih,
• Po-An Chen and
• Jeremy A. May

Beilstein J. Org. Chem. 2016, 12, 985–999, doi:10.3762/bjoc.12.97

• via C–H bond insertion by carbenes and nitrenes. Applications to natural product synthesis, a description of the essential elements in substrate-controlled reactions, and mechanistic details of transformations are presented. Overall, these transformations allow the construction of important ring

• systems rapidly and efficiently, though additional catalyst development is needed. Keywords: bridged rings; carbene; cascade reaction; C–H bond insertion; nitrene; Introduction Bridged polycyclic natural products are an inviting challenge to the synthetic chemist for their rich display of functional

• access to multiple targets from a single intermediate produced on large scale that may be stored until needed [17]. The C–H bond insertion has great potential as a method to access different polycyclic isomers (e.g., 1 or 3) through C–C or C–N bond formation from a carbene or nitrene, respectively

Recent advances in C(sp³)–H bond functionalization via metal–carbene insertions

• Bo Wang,
• Di Qiu,
• Yan Zhang and
• Jianbo Wang

Beilstein J. Org. Chem. 2016, 12, 796–804, doi:10.3762/bjoc.12.78

• (I) complexes. In some cases, high regioselectivity and enantioselectivity have been achieved in the C–H bond insertion of small alkanes. This review highlights the most recent accomplishments in this field. Keywords: alkane; diazo compounds; C–H bond functionalization; C–H bond insertion; metal

• allylic and benzylic sites and those at the α-position of oxygen or nitrogen, show high activity because of the stabilization of the partial positive charge developed in the transition state of the metal–carbene C–H bond insertion process. Such type of intramolecular metal–carbene C–H insertions shows

• the stabilizing effect of oxygen and nitrogen toward the positive charge development at the neighboring positions, the metal–carbene C–H bond insertions at these positions are favored. Davies and co-workers have recently reported a highly site-selective and enantioselective C–H bond insertion of

Recent advances in the gold-catalyzed additions to C–C multiple bonds

• He Huang,
• Yu Zhou and
• Hong Liu

Beilstein J. Org. Chem. 2011, 7, 897–936, doi:10.3762/bjoc.7.103

• examples of sp3 C–H bond insertion via a cationic gold(I)–carbenoid intermediate. 4.3 Cycloadditions Intramolecular [M + N]-type cycloaddition reactions are powerful tools for accessing complex molecular frameworks [98]. Several gold-catalyzed [3 + 2] [99], [4 + 2] [100][101][102][103][104][105], and [4

Intramolecular hydroxycarbene C–H-insertion: The curious case of (o-methoxyphenyl)hydroxycarbene

• Dennis Gerbig,
• David Ley,
• Hans Peter Reisenauer and
• Peter R. Schreiner

Beilstein J. Org. Chem. 2010, 6, 1061–1069, doi:10.3762/bjoc.6.121

• experiments (Scheme 1). Ring insertions characteristic for other singlet phenylcarbenes, i. e., phenylmethylcarbene [16] and phenylchlorocarbene [17], were not experimentally observed for 3, and we report herein the first C–H-bond insertion reaction of a hydroxycarbene that is akin to other heterocarbenes [18

• ][19][20] (Scheme 2). (o-Methoxyphenyl)hydroxycarbene (5) serves as the model compound for studying the intramolecular carbene C–H-bond insertion both under matrix isolation and solution conditions (Scheme 3). The generation of such carbenes in solution in high-boiling solvents would also provide