10147-11-2Relevant articles and documents
Single-compound libraries of organic materials: Parallel synthesis and screening of fluorescent dyes
Schiedel, Marc-Steffen,Briehn, Christoph A.,Baeuerle, Peter
, p. 4677 - 4680 (2001)
"Hits" with high quantum yields: The screening of the chromophores of a coumarin library for optical properties allowed the identification of "hits" with high fluorescence quantum yields (see picture) which could be used as fluorescence labels and laser dyes. The generation of the library was facilitated by an efficient method involving the parallel synthesis utilizing Pd-catalyzed cross-coupling reactions.
HIGHLY CHEMOSELECTIVE COUPLING REACTIONS OF ORGANOVANADIUM COMPOUNDS
Hirao, Toshikazu,Misu, Daisuke,Yao, Koichi,Agawa, Toshio
, p. 929 - 932 (1986)
Organovanadium compounds generated in dichloromethane from equimolar amounts of vanadium trichloride and Grignard reagents underwent the chemoselective cross-coupling reaction with acid chlorides leading to the corresponding ketones.Treatment with allyl halides resulted in allylation of organovanadium compounds.In the case of propargyl bromide, regioselective displacement occured to produce allene derivatives.
Palladium-catalyzed cross-coupling reaction of alkynylzincs with benzylic electrophiles
Qian, Mingxing,Negishi, Ei-Ichi
, p. 2927 - 2930 (2005)
The reaction of alkynylzinc bromides with benzyl bromides or chlorides in the presence of a catalytic amount of Pd(DPEphos)Cl2 in THF at 23°C cleanly produces the corresponding benzylated alkynes in 73-97% yields. With 10-3 mol % of Pd(DPEphos)Cl2, the maximum turnover number of 7.1 × 104 has been observed for the formation of PhCCCH2Ph.
Synthesis of acetylenes via dehydrobromination using solid anhydrous potassium phosphate as the base under phase-transfer conditions
Shenawi-Khalil, Sanaa,Sonavane, Sachin U.,Sasson, Yoel
, p. 2295 - 2297 (2012)
Phase-transfer catalyzed preparation of acetylenes from the corresponding vicinal dibromo compounds via double dehydrobromination using the mild solid base, anhydrous potassium phosphate, under very mild conditions is reported.
Chemo-, regio-, and stereoselective hydroboration of conjugated enyne alcohol/amine: Facile synthesis of Z,Z-/Z,E-1,3-dien-1/2-ylboronic ester bearing hydroxyl/amino group
Xu, Hua-Dong,Wu, Hao,Jiang, Chun,Chen, Peng,Shen, Mei-Hua
, p. 2915 - 2918 (2016)
Hydroboration of conjugated enyne alcohol/amine is studied by using copper salts and bis(pinacolato)diboron as pre-catalysts and boron source respectively. It is suggested that the chemo-selectivity is derived from a combined electronic influence of the heteroatoms on the substrate and the ligand on the transition metal. The regioselectivity is probably dominated mainly by electronic effect of the alkyne substituent. This study resulted in a highly selective protocol to access Z,Z-/Z,E-1,3-dien-1/2-ylboronic ester bearing hydroxyl/amino group.
Dehydrosilylation of Alkenylsilanes Utilizing Polyvalent Organoiodine Compounds
Ochiai, Masahito,Sumi, Kenzo,Nagao, Yoshimitsu,Fujita, Eiichi,Arimoto, Masao,Yamaguchi, Hideo
, p. 697 - 699 (1985)
Alkenylsilanes, on treatment with iodosylbenzene activated by co-ordination of boron trifluoride-diethyl ether to the oxygen atom, give the corresponding alkynes in good to excellent yields, presumably via vinyliodine(III) intermediates.
Acquiring and Exploiting Persistency of Propargyl Radicals: Novel Paradigms
Melikyan, Gagik G.,Davis, Ryan,Cappuccino, Samantha
, p. 2854 - 2867 (2016)
Three complementary methods for altering an intrinsic nature of propargyl radicals, from transient to persistent, were developed by fine-tuning the bulkiness and degree of substitution around the secondary and tertiary propargylic carbons, as well as by sterically enhancing a π-bonded Co2(CO)6 metal core. The latter was employed, as a mechanistic tool, for precluding an acetylene-allene rearrangement, stabilizing propargyl cations, and creating a steric hindrance that could provide for said transition from transient to persistent propargyl radicals. A window of opportunities was identified wherein the steric bulkiness in propargyl radicals remains below the persistency threshold , providing good to excellent stereoselectivities in radical dimerization reactions (d,l 62-100%). Along with the persistency threshold for tertiary propargyl radicals (278.2 ?3), two different thresholds for persistency in secondary propargyl radicals were established - 306.5 and 576.0 ?3 - dependent upon the molecular architecture and the nature of the substituents populating the radical centers. Three alternative molecular platforms were designed to exploit a newly acquired dichotomy in allylic radicals (α-persistent-γ-transient) and trichotomy in pentadienyl radicals (α-persistent-γ-transient-?-transient), providing access to molecular assemblies with contiguous 4°-4°, 4°-3°, and 3°-3° carbon atoms.
A Close-to-Aromatize Approach for the Late-Stage Functionalization through Ring Closing Metathesis
Lozhkin, Boris,Ward, Thomas R.
, (2021)
An efficient approach for the synthesis of monosubstituted aromatic compounds relying on a ring-closing metathesis followed by spontaneous 1,2-elimination is presented. The efficiency for late-stage functionalization is highlighted in various solvents (up to 920 TON). This approach is compatible with strained cycles and other multiple bonds in the substrate.
A general and versatile method for C-C cross-coupling synthesis of conjugated enynes: One-pot sequence starting from carbonyl compounds
Lyapkalo, Ilya M.,Vogel, Michael A. K.
, p. 4019 - 4023 (2006)
(Chemical Equation Presented) Ultimate coupling partners: Widely available enolizable aldehydes and ketones undergo Sonogashira cross-coupling with other carbonyl compounds to give conjugated enynes in a newly devised general method (see scheme; NfF = nonafluorobutane-1-sulfonyl fluoride). The synthetic protocol comprises at least four operating steps, which are carried out in one pot using common reagents, catalysts, and additives.
Lithium bis-(diisopropylamino)boracetylide [LiC≡C-B(ni-Pr2)2]. A new reagent for the preparation of terminal alkynes
Blanchard, Christiane,Vaultier, Michel,Mortier, Jacques
, p. 8863 - 8866 (1997)
Terminal alkynes RC≡CH [R = PhCO, PhCH2OCO, (CH3)2CHCH2OCO. Et2NCO. (EtO)2P(O), PhCH2, H2C=CH-CH2, and Ph-CH(OH)-] may be prepared in satisfactory yield in a one-pot process by reaction in THF at -78°C of the titled reagent with electrophiles followed by acidic workup with dilute HCl.
