Generation and cycloaddition of less- or non-stabilized azomethine ylides, or nitrile ylide equivalents, via unprecedented 1,4-stannatropy of N-(tributylstannylmethyl)thioamides were achieved. The reactions with dipolarophiles, such as electron-deficient alkenes and alkynes, afforded corresponding pyrrolidine and pyrrole derivatives effectively.

The synthesis of the compound that has been proposed to be the natural product sclerophytin F has been completed from a known vinylogous carbonate. The synthetic strategy relied upon rearrangement of a catalytically generated ylide-like intermediate to produce an oxabicyclo[6.2.1]-5-undecen-9-one and an intermolecular Diels-Alder reaction to construct the complete tricyclic core found in the na...

Lithiation of 1,2-dichloroor 1,2,3-trichloroferrocene with lithium tetramethylpiperidinide, followed by transmetallation with ZnCl2 and Pd(II)-catalyzed coupling with 2-bromopyridine, yield the pyridylferrocenes [CpFe{C5H2−nCl2+n(2-C5H4N)}] (2a, b, n = 0 or 1) as brown oils of low stability. Recrystallization of 2b produced a small number of X-ray quality crystals, which could be shown to have ...

Fifteen cyclic and acylic carbenes have been calculated with density functional theory at the BP86/def2-TZVPP level. The strength of the internal X→p(π) π-donation of heteroatoms and carbon which are bonded to the C(II) atom is estimated with the help of NBO calculations and with an energy decomposition analysis. The investigated molecules include N-heterocyclic carbenes (NHCs), the cyclic alky...

The development of new synthetic fluorination reactions has important implications in medicinal, agricultural, and materials chemistries. Given the prevalence and accessibility of alcohols, methods to convert alcohols to trifluoromethanes are desirable. However, this transformation typically requires four-step processes, specialty chemicals, and/or stoichiometric metals to access the trifluorom...

A highly efficient gold(I)-catalyzed Overman rearrangement of allylic trichloroacetimidates to allylic trichloroacetamides in water is reported. With this environmentally benign and scalable protocol, a series of C3-alkyl substituted allylic trichloroacetamides were synthesized in good to high yields.

1,3,4,5,6,11a-Hexahydro-7E-2-benzothionine 5, which is a [2,3] sigmatropic rearrangement product of 2-phenyltetrahydrothiopyranium 1-methylide 8, has been synthesized by reaction of 1-methyl-2phenyltetrahydrothiopyranium triflate 3 with sodium amide in liquid ammonia or by the fluoride ioninduced desilylation of trans-2-phenyl-1-[(trimethylsilyl)methyl]tetrahydrothiopyranium perchlorate trans-7...

Madhavan Jaccob , Gopal Sabapathi, J Vijaya Sundar, P Kolandaivel *, V Subramanian * & Ponnambalam Venuvanalingam * Theoretical and Computational Chemistry Laboratory, School of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, Tamil Nadu, India Email: [email protected] Chemical Laboratory, CSIR-Central Leather Research Institute, Adyar, Chennai 600 020, Tamil Nadu, India Ema...

A facile and efficient synthetic protocol was established for the construction of novel tri- and tetra-cyclic pyrrolo/pyrrolizinoquinoline architectures via the in situ formation of azomethine ylide followed by an intramolecular [3 + 2] cycloaddition reaction strategy. This protocol leads to the creation of two/three new rings and three/four contiguous stereocentres, in which one of them is a t...