The first palladium-catalyzed dearomative cyclization via a modified Catellani-type C-H functionalization has been realized. The new strategy led to a series of spiroindolenine derivatives bearing an all-carbon quaternary spirocenter from simple aryl halides and substituted indoles.

A modular system for the construction of radiometalated antibodies was developed based on the bioorthogonal cycloaddition reaction between 3-(4-benzylamino)-1,2,4,5-tetrazine and the strained dienophile norbornene. The well-characterized, HER2-specific antibody trastuzumab and the positron emitting radioisotopes (64)Cu and (89)Zr were employed as a model system. The antibody was first covalentl...

We report the surface-initiated growth of poly(alkylnorbornene) films via ring-opening metathesis polymerization (ROMP). The films are grown by exposure of a vinyl-terminated self-assembled monolayer (SAM) on gold to Grubbs first-generation catalyst and the subsequent exposure to an alkylnorbornene monomer. We investigate the influence of alkyl side chains on the structure, barrier, surface pro...

The bimetallic compound Na[W2(μ-Cl)3Cl4(THF)2]·(THF)₃ (1, {W (3) W}(6+), a'2e'4) is a highly efficient room-temperature initiator for ring opening metathesis polymerization (ROMP) of norbornene (NBE) and some of its derivatives. In most cases, addition of phenylacetylene (PA) as co-initiator improves the catalytic activity and retains the high cis-stereoselectivity. On the other hand, 1 can pol...

The tetrathioperrhenate anion, ReS4 (1), is shown to form adducts with a variety of alkenes. The alkene adducts form reversibly, and those of norbornene and norbornadiene were isolated. For norbornene, the Keq’s range from 12 000 (CH2Cl2 solution) to 2650 M-1 (pyridine solution). The following values were determined (MeCN soln): ∆H ) -53 kJ mol-1 and ∆S ) -98 J‚mol-1‚K-1. The solid-state struct...

Antioxidant norbornene-based monomers bearing biobased sterically hindered phenols (SHP)-NDF (norbornene dihydroferulate) and NDS (norbornene dihydrosinapate)-have been successfully prepared through biocatalysis from naturally occurring ferulic and sinapic acids, respectively, in presence of Candida antarctica Lipase B (Cal-B). The ring opening metathesis polymerization (ROMP) of these monomers...

Cycloaddition reactions involving tetrazines have proven to be powerful bioorthogonal tools for various applications. Conceivably, sequential and selective labeling using tetrazine-based reactions can be achieved by tuning the reaction rate. By varying the substituents on tetrazines, cycloaddition rate variations of over 200 fold have been achieved with the same dienophile. Upon coupling with d...

The reaction of [Re(H)(NO)2(PR3)2] complexes (1 a: R = PCy3; 1 b: R = PiPr3) with [H(OEt2)2][BAr(F)4] ([BAr(F)4] = tetrakis{3,5-bis(trifluoromethyl)phenyl}borate) in benzene at room temperature gave the corresponding cations [Re(NO)2(PR3)2][BAr(F)4] (2 a and 2 b). The addition of phenyldiazomethane to benzene solutions of 2 a and 2 b afforded the moderately stable cationic rhenium(I)-benzyliden...

Rare earth metal bis(alkyl) complexes attached by fluorenyl modified N-heterocyclic carbene (NHC) (Flu-NHC)Ln(CH(2)SiMe(3))(2) (Flu-NHC = (C(13)H(8)CH(2)CH(2)(NCHCCHN)C(6)H(2)Me(3)-2,4,6); Ln = Sc (2a); Y (2b); Ho (2c); Lu (2d)), ((tBu)Flu-NHC)Ln(CH(2)SiMe(3))(2) ((tBu)Flu-NHC = 2,7-(t)Bu(2)C(13)H(6)CH(2)CH(2)(NCHCCHN)C(6)H(2)Me(3)-2,4,6; Ln = Sc (1a); Lu (1d)) and attached by indenyl modified ...