Montmorillonite containing PdClp anchored via pendant phosphinated groups in the interlamellar region has been synthesized, characterized, and found t o hydrogenate terminal alkenes and al kynes selectively.

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Two photosystems are developed to harvest visible-light photons into electrons Via sequential electron transfer processes. Photosystem-A (PS-A) consisted of DCA as light harvesting electron acceptor and Ph 3 P as sacrificial electron donor, whereas photosystem-B (PS-B) employed DCA as usual electron acceptor, DMN as a primary electron donor, and ascorbic acid as a secondary and sacrificial electron donor. R,β-Unsaturated ketones are utilized as secondary electron acceptors. The design of these photosystems is based on the thermodynamic feasibility of electron transfer between each participating components. Electron transfer from DCA •-to R,β-unsaturated ketones leads to their β-activation as carbon centered radicals which cyclizes efficiently to tethered activated olefins. Cyclization with a nonactivated olefin is found to be moderate. The cyclization stereochemistries have been illustrated by studying the PET activation of 5 and 21. The exclusive trans-stereochemistry observed in 8 is explained by considering the thermodynamic equilibration of initially formed syn-intermediate 10 from 5. The isolation of trace amount of 9 in this reaction substantiates the syn-intermediacy as primary intermediate which is further confirmed by the isolation of 25 from 21. Formation of 25 suggests that wherever the syn-intermediate is thermodynamically more stable, it invariably undergoes further cyclization to geometrically well-placed enolate double bond. An interesting observation is made by isolating 9 as a major product from the PET activation of 5 using PS-B. Stabilization of 10 by ascorbic acid is suggested to be the plausible explanation for this unusual observation. Radicals produced by the reductive β-activation of R,β-unsaturated ketones follow well established radical cyclization rules which is exemplified by studying the reactions of 39 and 40. Generality of these cyclizations is demonstrated from the PET reactions of 29-32. Synthesis of 49, an important structural framework of biologically active angularly fused triquinanes, from 48 is included in this study to demonstrate the varied applicability of this strategy.

Photosensitized one-electron reductive activation of aldehydes/ketones tethered with activated olefins leads to efficient cyclization to give diastereoselective cycloalkanols in high yield. The activation is promoted by secondary and dark electron transfer from visible light (405 nm) initiated photosensitized electron transfer generated 9,10-dicyanoanthracene radical anion (DCA•-). The DCA•- is produced by electron transfer using either triphenylphosphine (Ph3P) as sacrificial electron donor (PS-A) or 1,5-dimethoxynaphthalene (DMN) as primary electron donor and ascorbic acid as sacrificial electron donor (PS-B), to light-absorbing DCA. The cyclization is suggested to involve ketyl radical intermediate. High trans diastereoselectivity is observed during the formation of cycloalkanols. This cyclization strategy is further extended for the stereoselective synthesis of optically pure C-furanoside (41), starting from naturally occuring l-tartaric acid. The stereochemistry of 41 is suggested based on the single-crystal X-ray diffraction data.