34052-66-9

Upstream product

• 75-89-8 2,2,2-trifluoroethanol 
• 93769-03-0 (Z)-1-methyl-2-<2-(1-propyn-1-yl)phenyl>vinyl triflate 
• 93769-24-5 1-<2-(1-Propin-1-yl)phenyl>-2-propanon 
• 615-42-9 1,2-Diiodobenzene 
• 74-99-7 prop-1-yne 
• 851758-56-0 (E,E)-bis-1,2-(2,2-dibromoethenyl)benzene 
• 74-88-4 methyl iodide 
• 583-53-9 2,3-dibromobenzene 
• 860556-20-3 1,2-bis-(1-bromo-propyl)-benzene 
• 33996-35-9 1,2-dipropenyl-benzene 
• 64-17-5 ethanol 
• 33996-36-0 1,2-bis-(1,2-dibromo-propyl)-benzene 

Downstream Products

• 33996-38-2 1,2-Dimethyl-8--3-<2-propin-(1)-yl-phenyl>-azulen 
• 33996-37-1 1,2-Dimethyl-4-3-<2-propin-(1)-yl-phenyl>-azulen 

Relevant academic research and scientific papers

Synthesis of Fulvene Vinyl Ethers by Gold Catalysis

Gold-catalyzed cyclization of 1,5-diynes with ketones as reagents and solvent provides diversely substituted vinyl ethers under mild conditions. The regioselectivity of such gold-catalyzed cyclizations is usually controlled by the scaffold of the diyne. H

Synthetic and mechanistic investigations on the rearrangement of 2,3-unsaturated 1,4-bis(alkylidene)carbenes to enediynes

The synthesis of 3,4-ene-1,5-diynes, the key structural moiety present in several naturally occurring antitumor antibiotics, from 1,2-enedialdehydes under two different experimental conditions is reported. One method involves the dibromomethylenation of dialdehydes under Corey-Fuchs conditions (CBr 4, Ph3P, and Zn) and treatment of the resulting tetrabromides with nBuLi or LDA to afford enediynes. The second method involves a base-mediated reaction of enedialdehydes with diethyl (1-diazo-2-oxopropyl) phosphonate (Bestmann-Ohira reagent) and subsequent transformation of the bis(diazo) compounds generated in situ to enediynes. While the transformation of bis(diazo) compounds to enediynes could take place exclusively through alkylidene-carbenes, generated in situ by geminal elimination of N2, an alternative pathway, involving the vicinal elimination of HBr to afford an intermediate bromoalkyne and its subsequent metal-halogen exchange and protonation during workup, exists for the bis(dibromoalkylidenes). However, our deuterium-labeling experiments with a model substrate, deuterated p-methoxybenzylidene dibromide, established the predominance of the alkylidenecarbenes, generated in situ by metal-halogen exchange and elimination, for this substrate and, by analogy, for the tetrabromides as well. The scope of this novel methodology was extended to the synthesis of various heteroatom-based (S, Se, and P) enediynes by quenching the acetylides with suitable electrophiles. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Synthesis of arenediynes via the vinylidenecarbene-acetylene rearrangement

A convenient method for the two-step synthesis of arenediynes from 1,2-arenedialdehydes is reported. Dibromomethylenation of dialdehydes under Corey-Fuchs conditions (CBr4, Ph3P, Zn) provides the tetrabromides in excellent yields. Treatment of the tetrabromides with n-BuLi or LDA affords 3,4-unsaturated 1,5-diynes, the key structural moiety present in several naturally occurring antitumour antibiotics, in varying yields. The key intermediates in these transformations appear to be vinylidenecarbenes or carbenoids, generated in situ via metal-halogen exchange and elimination.

An alkyne metathesis-based route to ortho-dehydrobenzannulenes

An application of alkyne metathesis to 1,2-di(prop-1-ynyl)arenes, producing dehydrobenzannulenes, is described. An efficient method for selective Sonogashira couplings of bromoiodoarenes under conditions of microwave irradiation is also reported.

Synthesis and Solvolysis of (Z)/(E)-1-Methyl-2-vinyl Triflate and 1-Methylene-2-ethyl Triflate

The synthesis and solvolysis of the triflates (Z)/(E)-8 and 20 in various solvents are described.The (E)-triflate 8 reacts in trifluoroethanol by rearrangement via the intermediate naphthyl cation 9 to give the naphthyl ether 22 and the naphthyl triflate