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
CAS Number
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.157.252
EC Number
  • 261-753-0
PubChem CID
UNII
CompTox Dashboard (EPA)
InChI
  • 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
SMILES
  • O(\C=C\C(O[Si](C)(C)C)=C)C
Properties
Chemical formula
 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:
Pictograms
 GHS02: FlammableGHS07: Exclamation mark
Signal word
 Warning
Hazard statements
 H226, H315, H319
Precautionary statements
 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 ?)
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.[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]

References

  1. ^ Sigma-Aldrich product page.
  2. ^ a b Sicherheitsdatenblatt Merck.
  3. ^ Danishefsky, Samuel J.; Kitahara, T. (1974). "Useful diene for the Diels-Alder reaction". J. Am. Chem. Soc. 96: 7807–7808. doi:10.1021/ja00832a031.
  4. ^ a b Strategic Applications of Named Reactions in Organic Synthesis, Laszlo Kurti,Barbara Czako, Elsevier 2005
  5. ^ Yuan, Yu (2002). "Acid-Free Aza Diels−Alder Reaction of Danishefsky's Diene with Imines". Organic Letters. 4: 3309–3311. doi:10.1021/ol0265822.
  6. ^ Loncaric, Catherine (2003). "Alkaline salt-catalyzed aza Diels–Alder reactions of Danishefsky's diene with imines in water under neutral conditions". Chemical Communications (5): 574–575. doi:10.1039/B300880K.
  7. ^ Node, Manabu (1996). "Exo selective Diels?Alder reaction of nitroolefins with Danishefsky's diene". Chemical Communications (22): 2559. 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. ^ This is an asymmetric reaction with a chiral ionic liquid as chiral solvent. The reported chemical yield is 66% with 60% diastereomeric excess
  11. ^ Simonsen, KB; Svenstrup, N; Roberson, M; Jorgensen, KA (2000). "Development of an unusually highly enantioselective hetero-Diels-Alder reaction of benzaldehyde with activated dienes catalyzed by hypercoordinating chiral aluminum complexes". Chemistry. 6: 123–8. PMID 10747395.
  12. ^ Yao, S; Saaby, S; Hazell, RG; Jorgensen, KA (2000). "Catalytic enantioselective aza-Diels-alder reactions of imines--an approach to optically active nonproteinogenic alpha-amino acids". Chemistry. 6: 2435–48. PMID 10939745.
  13. ^ Han, G; LaPorte, MG; Folmer, JJ; Werner, KM; Weinreb, SM (October 2000). "Total syntheses of the Securinega alkaloids (+)-14,15-dihydronorsecurinine, (-)-norsecurinine, and phyllanthine". J. Org. Chem. 65: 6293–306. PMID 11052071.
  14. ^ Janey, JM; Iwama, T; Kozmin, SA; Rawal, VH (2000). "Racemic and asymmetric Diels-Alder reactions of 1-(2-oxazolidinon-3-yl)-3-siloxy-1,3-butadienes". J Org Chem. 65: 9059–68. PMID 11149852.
  15. ^ Bernardelli, Patrick (2001). "Total Asymmetric Synthesis of the Putative Structure of the Cytotoxic Diterpenoid (−)-Sclerophytin A and of the Authentic Natural Sclerophytins A and B". Journal of the American Chemical Society. 123: 9021–9032. doi:10.1021/ja011285y.
  16. ^ Wang, Jing (2001). "A Straightforward Stereoselective Synthesis of d - and l -5-Hydroxy-4-hydroxymethyl-2-cyclohexenylguanine". The Journal of Organic Chemistry. 66: 8478–8482. doi:10.1021/jo015924z.
  17. ^ Yamashita, Yasuhiro (2003). "Chiral Hetero Diels−Alder Products by Enantioselective and Diastereoselective Zirconium Catalysis. Scope, Limitation, Mechanism, and Application to the Concise Synthesis of (+)-Prelactone C and (+)-9-Deoxygoniopypyrone". Journal of the American Chemical Society. 125: 3793–3798. doi:10.1021/ja028186k.
  18. ^ Du, Haifeng (2003). "Enantioselective Catalysis of Hetero Diels−Alder Reaction and Diethylzinc Addition Using a Single Catalyst". Organic Letters. 5: 1091–1093. doi:10.1021/ol034143c.
  19. ^ Ghosh, Arun K. (1996). "Asymmetric hetero Diels-Alder reactions of Danishefsky's diene and glyoxylate esters catalyzed by chiral bisoxazoline derived catalysts". Tetrahedron: Asymmetry. 7: 2165–2168. doi:10.1016/0957-4166(96)00261-3.
  20. ^ Zhao, Bei (2013). "Asymmetric Hetero-Diels–Alder Reaction of Danishefsky's Dienes with α-Carbonyl Esters Catalyzed by an Indium(III)–PyBox Complex". Organic Letters. 15: 2914–2917. doi:10.1021/ol400841s.
  21. ^ Wang, Bin (2002). "A Highly Enantioselective Hetero-Diels−Alder Reaction of Aldehydes with Danishefsky's Diene Catalyzed by Chiral Titanium(IV) 5,5',6,6',7,7',8,8'-Octahydro-1,1'-bi-2-naphthol Complexes". The Journal of Organic Chemistry. 67: 2175–2182. doi:10.1021/jo016240u.
  22. ^ Zheng, Jianfeng (2014). "Asymmetric Hetero-Diels-Alder Reaction of Danishefsky's Diene with α-Ketoesters and Isatins Catalyzed by a Chiral N , N′ -Dioxide/Magnesium(II) Complex". Chemistry - A European Journal. 20: 14493–14498. doi:10.1002/chem.201404144.
  23. ^ Amii, Hideki (2001). "Difluorinated Danishefsky's Diene: A Versatile C 4 Building Block for the Fluorinated Six-Membered Rings". Organic Letters. 3: 3103–3105. doi:10.1021/ol0163631.
This article is issued from Wikipedia. The text is available under Creative Commons Attribution-Share Alike 4.0 unless otherwise noted. Additional terms may apply for the media files.