William S. MacLachlan

3-Component palladium–indium mediated diastereoselective cascade allylation of imines with allenes and aryl iodidesElectronic supplementary information (ESI) available: experimental details. See http://www.rsc.org/suppdata/cc/b2/b202940e/

A new palladium–indium diastereoselective cascade allylation of imines using allenes and aryl iodides is described; N-tosyl and N-aryl homoallyl amines were obtained in moderate to good yields and excellent diastereoselectivity was observed when enantiomerically pure N-tert-butanesulfinyl imines were employed in the cascade.

Pictet–Spengler/Palladium Catalyzed Allenylation and Carbonylation Processes

Abstract The tactical combination of the Pictet–Spengler reaction with Pd catalyzed reactions with allene and with carbon monoxide provides rapid access to a range of tetrahydro-β-carboline and tetrahydroisoquinoline derivatives via intramolecular trapping of intermediate π-allyl– and acyl–palladium(II) complexes by the indolic or secondary amino moieties generating fused azepine and δ-lactam derivatives. Chiral tryptophan examples are also described.

Solid phase sequential 1,3-dipolar cycloaddition–Pictet–Spengler reactions

Abstract Up to six bonds and two rings can be created, in five component processes (five points of diversity), by AgOAc catalysed imine cycloaddition to Wang resin acrylate followed by Pictet–Spengler and Pd(0) catalysed reactions.

Diastereo- and regioselective palladium–indium bimetallic cyclisation–Barbier-type allylation cascades

Abstract A new diastereo -and regio selective Pd/In bimetallic cascade process which assembles three contiguous chiral centres is described. Pd(0)-catalysed cyclisation of aryl iodides onto proximate 1,3-dienes generates π-allylpalladium(II) species, transmetallation with indium and subsequent Barbier-type addition to aldehydes affords heterocyclic homoallylic alcohols.

Diastereoselective Pd/In bimetallic inter-intramolecular (class 2) cascade reactions of allenyl-imines and aryl iodides

Abstract A new diastereoselective Pd/In bimetallic inter–intramolecular cascade reaction employing allenyl-sulfinimines and aryl iodides is described. The tert-butanesulfinyl chiral auxiliary affords chiral, highly substituted cis-pyrrolidines and piperidines.

Sequential 1,3-Dipolar Cycloaddition-Pictet–Spengler Reactions. A Versatile Tactical Combination

Abstract The combination of thermal or Ag(I) catalysed imine→azomethine ylide→cycloaddition cascades with a subsequent Pictet–Spengler reaction allows the assembly of polyfunctional N-heterocycles, via formation of 4 bonds and 2 rings, in good yield.

Split-split. A multiple synthesiser approach to efficient automated parallel synthesis

Abstract A multiple synthesiser approach to high efficiency, high throughput synthesis is described. It involves eliminating duplication in multi-step synthesis by establishing a cascade of matched synthesisers in which each machine performs a single step and provides feedstocks for the next instrument. The utility of this approach is illustrated by the efficient construction of a large array by a 4 step solution synthesis.

Palladium catalysed tandem cyclisation–anion capture. Part 8: Cascade hydrostannylation—cyclisation–anion capture and cascade hydroboration—cyclisation–anion capture on solid phase

Abstract Up to four bonds and five stereocentres are created, in five component processes (five point diversity), utilising resin bound aryl iodides by hydroboration or hydrostannylation of alkynes, followed by cyclisation–anion capture involving Suzuki or Stille reactions. Three small libraries were prepared to validate the chemistry.

Synthesis of 16-decarboxy-16-hydroxymethyl amphotericin B - a novel antifungal agent

Abstract The synthesis of the novel polyene, 16-decarboxy-16-hydroxymethyl amphotericin B 5, the first monofunctionalised amphotericin B derivative without a carbonyl containing substituent in the C-16 position, is described. This primary alcohol 5, which shows negligible nephrotoxicity while maintaining good antifungal activity, was obtained via reduction of the novel N-Fmoc protected mycosamine containing derivative 8.

STEREOSELECTIVE SYNTHESIS OF 13-DEHYDROXY-(14S)-HYDROXYAMPHOTERICIN B METHYL ESTER

Abstract Stereoselective hydroboration of 6 affords, after further manipulation, 13-dehydroxy-(14 S )-hydroxyamphotericin B methyl ester 9 , the first amphotericin B derivative with a saturated ether function at C-13.