Synthesis and crystal structure of 5-carbaphosphatranes containing a four-membered cycle

Synthesis and steric structure of 3′,3′,5′-trimethyl-7′,7′-bis(trifluoromethyl)spiro[1,3,2-benzodioxaphosphole-2,1′-[2,6,8]trioxa[1λ5]phosphabicyclo[3.2.1]octane] and 3′,5′-dimethyl-7′,7′-bis(trifluoromethyl)spiro[1,3,2-benzodioxaphosphole-2,1′-[2,6,8]trioxa[1λ5]phosphabicyclo[3.2.1]oct[3]ene]

“…The orientation of substituents on the trigonal-bipyramidal five-coordinate phosphorus atom in 7 does not conform to their apicophilicities: the oxygen atoms occupy equatorial positions, while the carbon atoms are apical [11,12].…”

“…A five-coordinate phosphorus derivative with P-N bonds, 1,6,7-triphenyl-3,4 : 9,10-dibenzo-2,11-dioxa-5, 8 (11) in CCl 4 . This rearrangement can be regarded as a new method for the preparation of tricyclic cage phosphoranes (Scheme 3).…”

Reactions of 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-benzodioxaphosphepin-5-one with phenanthrenequinone and dibenzoyl

“…They are capable of being involved in cascade reactions with activated carbonyl compounds, Schiff bases, and ylidene derivatives of dicarbonyl compounds. In these reactions, the carbonyl group can participate in one or another step of the cascade process, leading to the formation of 1,3,2-dioxa(oxaza)-and 1,4,2-dioxa-(oxaza)phosphepines, 1,2-oxaphospholanes, and other difficultly accessible compounds [5][6][7][8][9][10][11][12].We recently showed that cyclic phosphorus(III) derivatives having an activated carbonyl group in the γ-position with respect to the phosphorus atom, e.g., 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-benzodioxaphosphepin-5-one (I), also undergo cascade transformations by the action of trichloroacetaldehyde and hexafluoroacetone. As a result, cage-like propeller phosphorane with a phosphorus-carbon bond (structure II) [13,14] or spiran structure III is formed; in the latter structure, the γ-carbonyl carbon atom becomes a spiro atom [15] (Scheme 1).…”

“…They are capable of being involved in cascade reactions with activated carbonyl compounds, Schiff bases, and ylidene derivatives of dicarbonyl compounds. In these reactions, the carbonyl group can participate in one or another step of the cascade process, leading to the formation of 1,3,2-dioxa(oxaza)-and 1,4,2-dioxa-(oxaza)phosphepines, 1,2-oxaphospholanes, and other difficultly accessible compounds [5][6][7][8][9][10][11][12].…”

An unusual cascade reaction of 4,5-dihydro-4,4-bis(trifluoromethyl)-2-phenyl-6,7-(4-chlorobenzo)[e]-1,3,2-dioxaphosphepin-5-one with chloral

“…The 5-carbaphosphatrane derivatives with pentacoordinated phosphorus atom, containing three oxygen atoms in equatorial sets and two less apicophilic carbon ones in apical sets were unexpectedly obtained in the reaction of compounds 1a,b with hexafluoroacetone. 9 In this work, we attempted to use chloral as another reactive compound for the synthesis of 5-carbaphosphatranes. However, the interaction of chloral with dioxaphosphepine 1b is more complex and proceeds by two main directions.…”