Danishefsky's diene

Danishefsky's diene
Names
Preferred IUPAC name
{[(3E)-4-Methoxybuta-1,3-dien-2-yl]oxy}trimethylsilane
Other names
Kitahara diene
trans-1-Methoxy-3-trimethylsilyloxy-buta-1,3-diene
(E)-1-Methoxy-3-trimethylsilyloxy-buta-1,3-diene
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.157.252
EC Number
  • 261-753-0
UNII
  • InChI=1S/C8H16O2Si/c1-8(6-7-9-2)10-11(3,4)5/h6-7H,1H2,2-5H3/b7-6+ Y
    Key: SHALBPKEGDBVKK-VOTSOKGWSA-N Y
  • InChI=1/C8H16O2Si/c1-8(6-7-9-2)10-11(3,4)5/h6-7H,1H2,2-5H3/b7-6+
    Key: SHALBPKEGDBVKK-VOTSOKGWBD
  • O(\C=C\C(O[Si](C)(C)C)=C)C
Properties
C8H16O2Si
Molar mass 172.299 g·mol−1
Density 0.89 g cm−3 (20 °C)
Boiling point 68 to 69 °C (154 to 156 °F; 341 to 342 K) at 0.0189 kPa
Hazards
GHS labelling:
Warning
H226, H315, H319
P210, P233, P240, P241, P242, P243, P264, P280, P302+P352, P303+P361+P353, P305+P351+P338, P321, P332+P313, P337+P313, P362, P370+P378, P403+P235, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Y verify (what is YN ?)
Infobox references

Danishefsky's diene (Kitahara diene) is an organosilicon compound and a diene with the formal name trans-1-methoxy-3-trimethylsilyloxy-buta-1,3-diene named after Samuel J. Danishefsky. Because the diene is very electron-rich it is a very reactive reagent in Diels-Alder reactions. This diene reacts rapidly with electrophilic alkenes, such as maleic anhydride. The methoxy group promotes highly regioselective additions. The diene is known to react with amines, aldehydes, alkenes and alkynes. Reactions with imines and nitro-olefins have been reported.

It was first synthesized by the reaction of trimethylsilyl chloride with 4-methoxy-3-buten-2-one and zinc chloride:

The diene has two features of interest: the substituents promote regiospecific addition to unsymmetrical dienophiles and the resulting adduct is amenable to further functional group manipulations after the addition reaction. High regioselectivity is obtained with unsymmetrical alkenes with a preference for a 1,2-relation of the ether group with the electron-deficient alkene-carbon. All this is exemplified in this aza Diels-Alder reaction:

In the cycloaddition product, the silyl ether is a synthon for a carbonyl group through the enol. The methoxy group is susceptible to an elimination reaction enabling the formation of a new alkene group.

Applications in asymmetric synthesis have been reported. Derivatives have been reported.

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