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Danishefsky's diene

Danishefsky's diene[1]
Structural formula of Danishefsky's diene
Ball-and-stick model of 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 Edit this at Wikidata
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+ checkY
    Key: SHALBPKEGDBVKK-VOTSOKGWSA-N checkY
  • 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)[2]
Boiling point 68 to 69 °C (154 to 156 °F; 341 to 342 K) at 0.0189 kPa[2]
Hazards
GHS labelling:
GHS02: FlammableGHS07: Exclamation mark
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).
checkY verify (what is checkY☒N ?)

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.[3][4] 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,[5] aldehydes, alkenes and alkynes.[4] Reactions with imines [6] and nitro-olefins [7] have been reported.

It was first synthesized by the reaction of trimethylsilyl chloride with 4-methoxy-3-buten-2-one and zinc chloride:[8]

Danishefsky's diene
Danishefsky's diene

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:[9][10]

Danishefsky's diene in Aza-Diels_Alder
Danishefsky's diene in Aza-Diels_Alder

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.[11][12][13][14][15][16][17][18][19][20][21][22] Derivatives have been reported.[23]

  1. ^ Sigma-Aldrich product page.
  2. ^ a b Sicherheitsdatenblatt Merck.
  3. ^ Cite error: The named reference Danishefsky was invoked but never defined (see the help page).
  4. ^ a b Cite error: The named reference Kurti was invoked but never defined (see the help page).
  5. ^ Cite error: The named reference Yuan2004 was invoked but never defined (see the help page).
  6. ^ Cite error: The named reference Loncaric was invoked but never defined (see the help page).
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  8. ^ Cite error: The named reference orgsynth was invoked but never defined (see the help page).
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  10. ^ Cite error: The named reference comment was invoked but never defined (see the help page).
  11. ^ Cite error: The named reference simonsen was invoked but never defined (see the help page).
  12. ^ Cite error: The named reference yao2000 was invoked but never defined (see the help page).
  13. ^ Cite error: The named reference han2000 was invoked but never defined (see the help page).
  14. ^ Cite error: The named reference iwama2000 was invoked but never defined (see the help page).
  15. ^ Cite error: The named reference Bernardelli was invoked but never defined (see the help page).
  16. ^ Cite error: The named reference wang2001 was invoked but never defined (see the help page).
  17. ^ Cite error: The named reference Yamashita was invoked but never defined (see the help page).
  18. ^ Cite error: The named reference du was invoked but never defined (see the help page).
  19. ^ Cite error: The named reference Ghosh was invoked but never defined (see the help page).
  20. ^ Cite error: The named reference Zhao2013 was invoked but never defined (see the help page).
  21. ^ Cite error: The named reference wang2002 was invoked but never defined (see the help page).
  22. ^ Cite error: The named reference zheng2014 was invoked but never defined (see the help page).
  23. ^ Cite error: The named reference amii was invoked but never defined (see the help page).
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