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Ylide
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Ylide
An ylide (/ˈɪlaɪd/) or ylid (/ˈɪlɪd/) is a neutral dipolar molecule containing a formally negatively charged atom (usually a carbanion) directly attached to a heteroatom with a formal positive charge (usually nitrogen, phosphorus or sulfur), and in which both atoms have full octets of electrons. The result can be viewed as a structure in which two adjacent atoms are connected by both a covalent and an ionic bond; normally written X+–Y−. Ylides are thus 1,2-dipolar compounds, and a subclass of zwitterions. They appear in organic chemistry as reagents or reactive intermediates.
The class name "ylide" for the compound should not be confused with the suffix "-ylide".
Many ylides may be depicted by a multiply bonded form in a resonance structure, known as the ylene form, while the actual structure lies in between both forms:[citation needed]
The actual bonding picture of these types of ylides is strictly zwitterionic (the structure on the right) with the strong Coulombic attraction between the "onium" atom and the adjacent carbon accounting for the reduced bond length. Consequently, the carbon anion is trigonal pyramidal.[citation needed]
Phosphonium ylides are used in the Wittig reaction, a method used to convert ketones and especially aldehydes to alkenes. The positive charge in these Wittig reagents is carried by a phosphorus atom with three phenyl substituents and a bond to a carbanion. Ylides can be 'stabilised' or 'non-stabilised'. A phosphonium ylide can be prepared rather straightforwardly. Typically, triphenylphosphine is allowed to react with an alkyl halide in a mechanism analogous to that of an SN2 reaction. This quaternization forms an alkyltriphenylphosphonium salt, which can be isolated or treated in situ with a strong base (in this case, butyllithium) to form the ylide.
Due to the SN2 mechanism, a less sterically hindered alkyl halide reacts more favorably with triphenylphosphine than an alkyl halide with significant steric hindrance (such as tert-butyl bromide). Because of this, there will typically be one synthetic route in a synthesis involving such compounds that is more favorable than another.
Phosphorus ylides are important reagents in organic chemistry, especially in the synthesis of naturally occurring products with biological and pharmacological activities. Much of the interest in the coordination properties of a-keto stabilized phosphorus ylides stems from their coordination versatility due to the presence of different functional groups in their molecular structure.
The a-keto stabilized ylides derived from bisphosphines like dppe, dppm, etc., viz., [Ph2PCH2PPh2]C(H)C(O)R and [Ph2PCH2CH2PPh2]C(H)C(O)R (R = Me, Ph or OMe) constitute an important class of hybrid ligands containing both phosphine and ylide functionalities, and can exist in ylidic and enolate forms. These ligands can therefore be engaged in different kinds of bonding with metal ions like palladium and platinum.
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Ylide
An ylide (/ˈɪlaɪd/) or ylid (/ˈɪlɪd/) is a neutral dipolar molecule containing a formally negatively charged atom (usually a carbanion) directly attached to a heteroatom with a formal positive charge (usually nitrogen, phosphorus or sulfur), and in which both atoms have full octets of electrons. The result can be viewed as a structure in which two adjacent atoms are connected by both a covalent and an ionic bond; normally written X+–Y−. Ylides are thus 1,2-dipolar compounds, and a subclass of zwitterions. They appear in organic chemistry as reagents or reactive intermediates.
The class name "ylide" for the compound should not be confused with the suffix "-ylide".
Many ylides may be depicted by a multiply bonded form in a resonance structure, known as the ylene form, while the actual structure lies in between both forms:[citation needed]
The actual bonding picture of these types of ylides is strictly zwitterionic (the structure on the right) with the strong Coulombic attraction between the "onium" atom and the adjacent carbon accounting for the reduced bond length. Consequently, the carbon anion is trigonal pyramidal.[citation needed]
Phosphonium ylides are used in the Wittig reaction, a method used to convert ketones and especially aldehydes to alkenes. The positive charge in these Wittig reagents is carried by a phosphorus atom with three phenyl substituents and a bond to a carbanion. Ylides can be 'stabilised' or 'non-stabilised'. A phosphonium ylide can be prepared rather straightforwardly. Typically, triphenylphosphine is allowed to react with an alkyl halide in a mechanism analogous to that of an SN2 reaction. This quaternization forms an alkyltriphenylphosphonium salt, which can be isolated or treated in situ with a strong base (in this case, butyllithium) to form the ylide.
Due to the SN2 mechanism, a less sterically hindered alkyl halide reacts more favorably with triphenylphosphine than an alkyl halide with significant steric hindrance (such as tert-butyl bromide). Because of this, there will typically be one synthetic route in a synthesis involving such compounds that is more favorable than another.
Phosphorus ylides are important reagents in organic chemistry, especially in the synthesis of naturally occurring products with biological and pharmacological activities. Much of the interest in the coordination properties of a-keto stabilized phosphorus ylides stems from their coordination versatility due to the presence of different functional groups in their molecular structure.
The a-keto stabilized ylides derived from bisphosphines like dppe, dppm, etc., viz., [Ph2PCH2PPh2]C(H)C(O)R and [Ph2PCH2CH2PPh2]C(H)C(O)R (R = Me, Ph or OMe) constitute an important class of hybrid ligands containing both phosphine and ylide functionalities, and can exist in ylidic and enolate forms. These ligands can therefore be engaged in different kinds of bonding with metal ions like palladium and platinum.