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Synlett 2009(4): 554-557  
DOI: 10.1055/s-0028-1087916
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Thieme Chemistry Journal Awardees - Where are They Now? Catalytic Transport with an Amine Carrier in a Fluorous Triphasic Reaction

Vittorio Montanaria, Marvin S. Yu*a, Dennis P. Curran*b
a Fluorous Technologies, Inc., UPARC, 970 William Pitt Way, Pittsburgh, PA 15238, USA
Fax: +1(412)9656448; e-Mail: myu@fluorous.com;
b Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA
e-Mail: curran@pitt.edu;
Further Information

Publication History

Received 1 August 2008
Publication Date:
16 February 2009 (online)

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Abstract

Several aromatic aldehydes are transported by a fluorous amine from one organic phase through a fluorous phase to another organic phase. The derived imines react with phenylhydrazine to immobilize the transported product as a hydrazone and release the amine for reuse. In this way, catalytic transport is accomplished for the first time.

Key words

triphasic reaction - transport - fluorous chemistry - U-tube - fluorous amine

    References and Notes

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1

DPC holds an equity interest in Fluorous Technologies, Inc.

5

The controls were conducted similarly to the transport experiments. Aldehydes were vortexed with 1 equiv of amine or hydrazine for 1 h in MeCN. Formation of the imine or hydrazone was quantitative as assayed by GC. These samples then served as standards for the transport experiments.

7

The Kp ([FC-72]/[CH3CN]) of 3 and 5 were measured by direct partitioning as 2.3 and 0.8, respectively.

8

About 5-10% of the volume of the FC-72 phase was lost in each cycle, presumably due to evaporation. This was made up by adding additional FC-72 at the beginning of each new cycle to return the volume to 7 mL.

9

We also considered that transport of the aldehyde might occur by accidental transfer of some of the organic source phase to the receiving phase during the cycles. But we did not observe back transfer of the hydrazine or hydrazone, so this seems unlikely.