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Efficient Syntheses of Fluorous Primary Phosphines that Do Not Require PH3.

Authors :: Emnet, Charlotte
Gladysz, J. A.
Source :: Synthesis; 2005, Vol. 2005 Issue 6, p1012-1018, 7p
Publication Year :: 2005
Abstract: Arbuzov reactions of the fluorous primary iodides R<subscript>fn</subscript>(CH<subscript>2</subscript>)<subscript>m</subscript>I [R<subscript>fn</subscript> = CF<subscript>3</subscript>(CF<subscript>2</subscript>)<subscript>n-1</subscript>; n/m = 6/2, 8/2, 8/3, 10/2] and P(OEt)<subscript>3</subscript> (excess, 160 °C) give the fluorous phosphonates R<subscript>fn</subscript>(CH<subscript>2</subscript>)<subscript>m</subscript>P(O)(OEt)<subscript>2</subscript> (56-59%), which are reduced with LiAlH<subscript>4</subscript> to the title compounds R<subscript>fn</subscript>(CH<subscript>2</subscript>)<subscript>m</subscript>PH<subscript>2</subscript> (62-78%). Fluorophilicities (CF<subscript>3</subscript>C<subscript>6</subscript>F<subscript>11</subscript>/toluene partition coefficients) increase with the length of the R<subscript>fn</subscript> moiety, decrease with the length of the (CH<subscript>2</subscript>)<subscript>m</subscript> moiety, and decrease in the functional group sequence R<subscript>fn</subscript>(CH<subscript>2</subscript>)<subscript>m</subscript>NH<subscript>2</subscript> > R<subscript>fn</subscript>(CH<subscript>2</subscript>)<subscript>m</subscript>PH<subscript>2</subscript> > R<subscript>fn</subscript>(CH<subscript>2</subscript>)<subscript>m</subscript>P(O)(OEt)<subscript>2</subscript>. [ABSTRACT FROM AUTHOR]