Acetylenes, biaryl

S. Yamaguchi and T.M. Swager, Oxidative cyclization of bis(biaryl)acetylenes synthesis and photophysics of dibcnzo, /j]chrysene-based fluorescent polymers, J. Am. Chem. Soc., 123 12087-12088, 2001. 

Overview. The proposed near-term research is divided into three areas, which will be pursued simultaneously. The first is the complete characterization of the current mercury-responsive fluorescent chemosensor system, including the measurement of fluorescence lifetimes, to discern the origin of the conformational control of fluorescence. The second is to develop two classes of substituted biaryl acetylenic fluorescent chemosensors, to move the observed fluorescence into the visible region and increase the magnitude of the fluorescence signal, which occurs upon conformational restriction. 

For the alkylation and alkenylation of C-H bonds, olefins and acetylenes are used as reactants. This type of coupling protocol is not applicable to arylation. Recently, a nitrogen-directed arylation of aromatic C-H bonds, leading to biaryl compounds has been developed. In 2001, Oi demonstrated that ruthenium(II)-phosphine can be used as a catalyst in the regioselective arylation of 2-arylpyridines using aryl halides (Eq. 9.34) [4 ]. The predominant ortho selectivity indicates that the coordination of... 

In the presence of a catalytic amount of PdCh, Ar>,BiX2 (X=C1, OAc) couples with arylstannanes to give biaryls (Scheme 14.155) or, under a CO atmosphere, diaryl ketones (Scheme 14.156) [316]. Unsymmetrical biaryls are also prepared by Pd-catalyzed reaction of diaryliodonium salts with Ar3BiX2 [317]. Terminal acetylenes are phenylated by Ph3BiF2 under CuCl catalysis to afford phenyl-substituted acetylenes [318]. 

Coupling of terminal acetylenes with 3-chloropyridazines has been performed, using the Pd -Cu -EtjNH system, giving 3-(alkynyl)pyridazines in yields of up to 78% phenylacetylene gives (90) with 3-chloropyridazine 1-oxide but only gives tars with the isomeric 2-oxide/ 3-(Alkynyl)cinnolines have been similarly prepared from 3-iodo- and 3-bromo-cinnolines, and attempts to couple alkenes have been reported it is not unusual, in this type of reaction, to obtain small amounts of homo-coupling products i.e. biaryls), but an excellent yield of 3,3 -bicinnolinyl (81%) was obtained from 3-bromo-cinnoline and styrene. 

The quadratic NLO active molecules are mostly based on donor-acceptor substituted aromatics benzene, stil-benes, diaryl acetylenes, diacetylenes, and biaryls are commonly used frameworks. In addition to the above materials, many more organic and organometallic compounds were examined by the powder SHG method, or their molecular hyperpolarizabilities were measured using EFISHG/HRS techniques, or both.t >... 

Endogenous small molecules such as phosphoserine and ATRA were also found to promote neural differentiation. Although ATRA has been shown to promote neurogenesis in vivo it shows relatively low levels of efficiency in vitro, and is also unstable upon irradiation. In an attempt to circumvent this problem, Christie et al. prepared stable ATRA mimics based on biaryl acetylenes. Intriguingly, /jara-substituted 4a was observed to give rise to a neural phenotype in vitro, but the corresponding meta-isomer 4b was observed to give primarily epithelial phenotype upon treatment of the same precursor cells. 

Tandem cycloaddition of diiodotetrayne 162 with acetylene resulted in the efficient formation of 4,4 -diiodobiaryl 163 in 87% yield (Scheme 3.34) [49]. This novel biaryl building block was further subjected to cross coupling with p-biarylboronate... 

Axially chiral biaryls are found widely in the key structure of useful chiral ligands and catalysts [1] and biologically active compounds [2], The conventional method for their catalytic asymmetric synthesis is based on an asymmetric cross-coupling approach [3], As a conceptually new approach to axially chiral biaryls, asymmetric aromatic ring construction via transition-metal-catalyzed [2 - - 2 + 2] cycloaddition has recently appeared [4], In 1999, Sato et al. reported two types of nickel-catalyzed [2-1-2-1-2] cycloaddition for the synthesis of functionalized biaryls [5], One was the cycloaddition of aryl-substituted monoyne 1 with acetylene, leading to biaryl 2 (Scheme 9.1), and the other was the cycloaddition of aryl-substituted 1,6-diyne 3 with acetylene, leading to biaryl 4 (Scheme 9.2) [5],... 

Heller et al. applied the methodology above to the enantioselective synthesis of axially chiral biaryl monophosphine ligands. The reactions of alkynylphosphine oxides 11 with acetylene in the presence of the chiral cyclopentadienyl cobalt(I) catalyst... 

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