Homolytic substitution at phosphorus for C–P bond formation in organic synthesis

• Hideki Yorimitsu

Beilstein J. Org. Chem. 2013, 9, 1269–1277, doi:10.3762/bjoc.9.143

• phosphorus always culminates in difunctionalization of a multiple bond. Therefore this methodology will find application in the synthesis of complex phosphines including bidentate ones. Radical substitution of halogen in organic halide with phosphorus will be an alternative to classical ionic substitution

Metal–ligand multiple bonds as frustrated Lewis pairs for C–H functionalization

• Matthew T. Whited

Beilstein J. Org. Chem. 2012, 8, 1554–1563, doi:10.3762/bjoc.8.177

• demonstrate that the resultant reactivity may be a powerful tool for the functionalization of C–H and E–H bonds. Keywords: ambiphilic reactivity; C–H activation; C–H functionalization; frustrated Lewis pair; metal carbene; multiple bond; Introduction Orbital cooperation has long been recognized as an

• heterocumulenes [71]. Reductive coupling of two CS2 units at (PNP)Ir═C(H)Ot-Bu [73]. Possible routes to C–H functionalization by 1,2-addition across a polarized metal–element multiple bond. Alkoxycarbene formation by double C–H activation at (PNP)Ir [88]. Catalytic oxidation of MTBE by multiple C–H activations

Amines as key building blocks in Pd-assisted multicomponent processes

• Didier Bouyssi,
• Nuno Monteiro and
• Geneviève Balme

Beilstein J. Org. Chem. 2011, 7, 1387–1406, doi:10.3762/bjoc.7.163

• coupling of aryl chlorides. This was followed by an intramolecular alkyne–hydroamination (addition of an N–H bond across a carbon–carbon multiple bond) leading to the corresponding indole derivatives 52. The amination/alkyne–hydroamination sequence requires the addition of 1.5 equiv of t-BuOK to reach

Multicomponent reaction access to complex quinolines via oxidation of the Povarov adducts

• Esther Vicente-García,
• Rosario Ramón,
• Sara Preciado and
• Rodolfo Lavilla

Beilstein J. Org. Chem. 2011, 7, 980–987, doi:10.3762/bjoc.7.110

• single quantum coherence) and long-range 1H,13C-COSY (HMBC: heteronuclear multiple bond connectivity). IR spectra were recorded using a Thermo Nicolet Nexus spectrometer and are reported in wavenumbers (cm−1). High resolution mass spectrometry was performed by the University of Barcelona Mass

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

• catalytic addition of a nitrogen nucleophile to a C–C multiple bond represents an attractive approach to the formation of C–N bonds [55]. This is a direct and efficient procedure for the synthesis of nitrogen containing compounds of industrial importance. 3.1 Alkyl- and aromatic amines as nucleophiles

The catalytic performance of Ru–NHC alkylidene complexes: PCy₃ versus pyridine as the dissociating ligand

• Stefan Krehl,
• Diana Geißler,
• Sylvia Hauke,
• Oliver Kunz,
• Lucia Staude and
• Bernd Schmidt

Beilstein J. Org. Chem. 2010, 6, 1188–1198, doi:10.3762/bjoc.6.136

• if the pyridine complex H is used as a catalyst. For other examples, we have previously observed that benzyl ether moieties in close proximity to a C–C-multiple bond retard or inhibit metathesis reactions [50]. Presumably, partial catalyst deactivation by coordination of the benzyloxy group to the