Phosphines have, in combination with transition metals, played a pivotal role in the rapid development of efficient catalytic processes. Caged phosphines constitute a class of three-dimensional scaffolds providing unique control over steric and electronic properties. The versatility of the caged phosphine ligands has been demonstrated elegantly by the groups of Verkade, Gonzalvi as well as Stradiotto. Our research group has also been working extensively for the past several years in the development of 1,3,5-triaza-7-phosphaadamantane-based caged ligands and in this personal note we have summarized these applications pertaining to the modification of biologically useful nucleosides and heteroarenes.
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http://dx.doi.org/10.1002/tcr.202000109 | DOI Listing |
Adv Carbohydr Chem Biochem
November 2024
Institute of Organic Chemistry, Polish Academy of Sciences, Warsaw, Poland.
Sucrose, an inexpensive starting material available in virtually unlimited quantities, affords entry into a variety of novel and useful carbohydrate compounds. Selective protection of the secondary hydroxyl groups gives rise to a group of O-benzyl-protected intermediates that are useful in the synthesis of chiral phosphines and amino compounds of interest in the study of biological systems. The benzyl-protected fine chemicals are also key components in the synthesis of crown, thia-crown, and aza-crown compounds.
View Article and Find Full Text PDFInorg Chem
September 2024
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str., 28, 119991 Moscow, Russia.
A series of structurally similar trinuclear macrocyclic copper(I) and silver(I) pyrazolate complexes bearing various short-bite diphosphine RPCH(R')PR ligands are reported. Upon diphosphine coordination, the planar geometry of the initial complexes undergoes bending along the line between two metal atoms coordinated to the phosphorus moieties. The complexes based on dcpm ligands (R = cyclohexyl, R' = H, Ph) do not exhibit dynamic behavior in solution at room temperature on the P NMR time scale as it was previously observed for similar trinuclear copper complexes bearing the dppm (R = Ph, R' = H) scaffold.
View Article and Find Full Text PDFJ Am Chem Soc
September 2024
Department of Chemistry & Biochemistry, University of California San Diego, La Jolla, California 92093, United States.
Polymeric materials bearing Frustrated Lewis Pair (FLP) functionality are promising candidates for use as heterogeneous catalysts and adaptive materials, but synthetic access to FLP-functional polymers remains limited due to the incompatibility of FLPs with standard polymerization chemistries. Herein, we describe a synthetic approach that "cages" highly reactive vicinal phosphine-borane FLPs as covalent alkene adducts, which are stable to Ni-mediated vinyl addition polymerization. We discovered that the caged FLP adducts can be photochemically activated to liberate vicinal FLPs, enabling spatiotemporally controlled release of FLPs from polymeric precursors.
View Article and Find Full Text PDFChem Commun (Camb)
August 2024
Department of Chemistry, Western University, 1151 Richmond Street, London, ON, N8K 3G6, Canada.
Boraadamantanes are a privileged class of caged group 13 compounds having a trigonal pyramidal (non-VSEPR) ground-state. The Lewis acid-base chemistry of this type of compound is underdeveloped when compared to acyclic derivatives. This report provides the first examples of bifunctional boraadamantanes with an appended phosphine moiety (also the first boraadamantanes having a phosphorus-boron bond).
View Article and Find Full Text PDFACS Macro Lett
July 2024
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200433, China.
Great effort has been dedicated to the engineering of porous organic cages (POCs) in geometry and topology. Yet, harnessing these cage-like entities as premade building units to construct infinite cage-based superstructures remains elusive. In this study, we design a type of vertex-modified phosphine organic prism by a postfunctionalized approach and use it as a ditopic cage monomer to achieve an intercage supramolecular polymerization via the synergy of metal coordination and π-π dimerization.
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