Danishefsky's diene

Source: Wikipedia, the free encyclopedia.
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

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

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

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]

References

  1. ^ Sigma-Aldrich product page.
  2. ^ a b Sicherheitsdatenblatt Merck.
  3. doi:10.1021/ja00832a031
  4. ^ a b Strategic Applications of Named Reactions in Organic Synthesis, Laszlo Kurti,Barbara Czako, Elsevier 2005
  5. doi:10.1021/ol0265822
  6. doi:10.1039/B300880K
  7. doi:10.1039/CC9960002559
  8. ^ Preparation and Diels-Alder Reaction of a Highly Nucleophilic Diene. Org. Synth., Coll. Vol. 7, p.312 (1990); Vol. 61, p.147 (1983). Link
  9. ^ Asymmetric aza-Diels-Alder reaction of Danishefsky's diene with imines in a chiral reaction medium Pegot B, Nguyen Van Buu O, Gori D, Vo-Thanh G Beilstein Journal of Organic Chemistry, 2006 Link Archived 2006-10-11 at the Wayback Machine
  10. diastereomeric excess
  11. ^ Development of an unusually highly enantioselective hetero-Diels-Alder reaction of benzaldehyde with activated dienes catalyzed by hypercoordinating chiral aluminum complexes Simonsen KB1, Svenstrup N, Roberson M, Jorgensen KA. Chemistry. 2000 Jan;6(1):123-8.
    PMID 10747395
  12. PMID 10939745
  13. PMID 11052071
  14. PMID 11149852
  15. doi:10.1021/ja011285y
  16. doi:10.1021/jo015924z
  17. doi:10.1021/ja028186k
  18. doi:10.1021/ol034143c
  19. doi:10.1016/0957-4166(96)00261-3
  20. doi:10.1021/ol400841s
  21. doi:10.1021/jo016240u
  22. doi:10.1002/chem.201404144
  23. doi:10.1021/ol0163631
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