Multivalent Activation in Temporary Phosphate Tethers:  A New Tether for Small Molecule Synthesis

Abstract

[reaction: see text]. A new tether for small molecule synthesis is reported. This functionally active tether mediates the desymmetrization of a pseudo-C(2)-symmetric tris-allylic phosphate triester to generate a P-chiral bicyclo[4.3.1]phosphate containing ample steric and stereoelectronic differentiation for investigating chemo-, regio-, and stereoselective transformations. Overall, the method reported herein demonstrates a fundamentally new role of phosphates in synthesis and provides differentiated polyol building blocks for use in natural product synthesis.

Transition metals in organic synthesis: Highlights for the year 2005

“…A large variety of ring systems were prepared via alkene-alkene RCM using ruthenium catalysts [441] including, furans and pyrroles [1062], macrocycles [1063][1064][1065][1066][1067][1068][1069][1070][1071], five-to nine-membered unsaturated cyclic amines [498,519,898,[1072][1073][1074][1075][1076][1077], cyclooctenes [1078], chiral azepin-3-ols and azocin-3-ols [1079], oxepinand oxocin-annulated 2-quinolones [1080], benzazepines [1081,1082], 1-azaspiro [5.5]undacanes [1083], N-sulfonyl-2-quinolinones [1084], bis(silyl)- [3]-ferrocenophanes [1085], ferroceno-quinolines and -isoquinolines [1086], polycyclic hydrocarbons [1087], cyclic ␣-arylthiophosphonate esters [1088], carbohydrate-based macrolides [1089], fused carbazoles [157], 4-methyl-5-alkyl-2(5H)-furanones [1090], bibicyclo [8.8.8]hexacosanes [1091], bicyclic imidazoles [1092], bicyclic phosphates [1093], bicyclic lactams [1094], hexofuranose-like imino sugars [1095], C8-glycomimeti...…”

Reaction of Tetrahydropyranyl Ethers with Triethylsilyl Trifluoromethanesulfonate–2,4,6‐Collidine Combination: Speculation on the Intermediate, Efficient Deprotection, and Application to Efficient Ring‐Closing Metathesis as a Tether

“…Recently, another efficient methodology using phosphate tethers has been reported. [7] We present here a novel tether methodology using the THP unit as a tether.…”

Synthesis of cyclic 1,3-diols as scaffolds for spatially directed libraries

“…The four stereoisomers of mono-TIPS protected cyclopentanediol 3 were prepared from 2 8 by the straightforward modification of our previously published route to 4-silyloxy-cyclopenten-2-ones (Scheme 1a). 9 The diols were prepared and used as TIPS derivatives to ensure stepwise substitution of the cyclopentenediols by diversifying groups.…”