Catalytic Hydrofunctionalization Reactions of 1,3-Diynes

Abstract

Metal-catalyzed hydrofunctionalization reactions of alkynes, i.e., the addition of Y–H units (Y = heteroatom or carbon) across the carbon–carbon triple bond, have attracted enormous attention for decades since they allow the straightforward and atom-economic access to a wide variety of functionalized olefins and, in its intramolecular version, to relevant heterocyclic and carbocyclic compounds. Despite conjugated 1,3-diynes being considered key building blocks in synthetic organic chemistry, this particular class of alkynes has been much less employed in hydrofunctionalization reactions when compared to terminal or internal monoynes. The presence of two C≡C bonds in conjugated 1,3-diynes adds to the classical regio- and stereocontrol issues associated with the alkyne hydrofunctionalization processes’ other problems, such as the possibility to undergo 1,2-, 3,4-, or 1,4-monoadditions as well as double addition reactions, thus increasing the number of potential products that can be formed. In this review article, metal-catalyzed hydrofunctionalization reactions of these challenging substrates are comprehensively discussed.

Synthesis, crystal structure, Hirshfeld surface analysis and DFT study of the 1,1′-(buta-1,3-diyne-1,4-diyl)bis(cyclohexan-1-ol)

“…The presence of two triple C C bonds and two hydroxy groups in the molecules of diacetylene diols R 1 R 2 (OH)C-C C-C C-C(OH)R 3 R 4 , as well as substituents with different structures and functional groups containing heteroatoms, increases the possibilities of synthesis and the production of valuable, chemically stable and biologically active compounds based on such compounds (Cadierno, 2022). In particular, as the hydrogen atom adjacent to the strong C C bond is labile (Bru ¨cner, 2010), terminal alkynes easily undergo nucleophilic addition reactions to the carbonyl group and terminal (Hosseini et al, 2020;Sum et al, 2013) or internal acetylene alcohols (Tanaka et al, 2011;Motoki et al, 2007) and diols (Ardila-Fierro et al, 2019) with various substituents.…”

Terminal Atsetilen Spirtlarining Oksidlanishi Asosida Diindiollar Sintezi

“…Terminal atsetilen spirtlari tarkibidagi C≡C ning bog' uzunligi oddiy sigma bog'ga nisbatan qisqa bo'lib, bog' energiyasi yuqori bo'lishi hisobiga vodorodning harakatchanligi ortadi va sp-s bog'ning oson uzilishiga sabab bo'ladi [15]. Tadqiqot obʼekti sifatida olingan terminal atsetilen spirtlarining oksidlanish bilan boradigan birikish reaksiyasi amalga oshirish uchun katalizator sifatida mis (I)-xlorid, ligand sifatida N,N,Nˊ,Nˊ -tetrametiletilendiamin (TMEDA), promator tetraxlorometan (CCl4) va erituvchi metanol (MeOH) yordamida diatsetilen diollari, yaʼni molekulasida ikkita uch bog' va ikkita gidroksil guruhi hamda turli xil o'rinbosarlar saqlagan yangi avlod organik birikmalar sintez qilindi.…”

Regioselective Cobalt(II) Catalyzed C–H Functionalization and [3 + 2] Annulation of N-Arylguanidines with 1,3-Diynes

“…11a,b, 12 1,3-Diynes are key building blocks in organic chemistry. 13,14 When 1,3-diynes are used as substrates in C�H functionalization/annulation, one encounters more challenges such as chemoselectivity between two alkynyl units, regioselectivity, and selective formation of monoversus bis-heterocycles. 15,16 Glorius and co-workers first reported Cp*Rh(III) catalyzed redox neutral C�H functionalization and annulation reactions of N-(pivaloyloxy)benzamides with 1,3-diynes to afford monoalkynylated heterocycles and bis-heterocycles.…”

“…Alkynyl indoles are an important class of heterocyclic compounds, due to their role as precursors for annulated indoles and bis-heterocycles. ,, 1,3-Diynes are key building blocks in organic chemistry. , When 1,3-diynes are used as substrates in CH functionalization/annulation, one encounters more challenges such as chemoselectivity between two alkynyl units, regioselectivity, and selective formation of mono- versus bis-heterocycles. , Glorius and co-workers first reported Cp*Rh­(III) catalyzed redox neutral CH functionalization and annulation reactions of N -(pivaloyloxy)­benzamides with 1,3-diynes to afford monoalkynylated heterocycles and bis-heterocycles . Following Glorius’ approach, several researchers used substrates that contain reactive NO, − CN, NCl, and NN bonds and >CS­(O)­Me 2 bonds as internal oxidants in CH functionalization/1,3-diyne annulation catalyzed by Co­(II) salt, Cp*M­(III) (M = Rh and Co) and (η 6 - p -cymene)­Ru­(II) precursors.…”