Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2014 Jun 20;16(12):3320-3.
doi: 10.1021/ol501329t. Epub 2014 Jun 11.

Synthesis of isochromene-type scaffolds via single-flask Diels-Alder-[4 + 2]-annulation sequence of a silyl-substituted diene with menadione

Jihoon Lee  1 , James S Panek
Affiliations

Synthesis of isochromene-type scaffolds via single-flask Diels-Alder-[4 + 2]-annulation sequence of a silyl-substituted diene with menadione

Jihoon Lee et al. Org Lett. .

Abstract

A sequential Diels-Alder reaction/silicon-directed [4 + 2]-annulation was developed to assemble hydroisochromene-type ring systems from menadione 2. In the first step, a Diels-Alder of the 1-silyl-substituted butadiene 1 with 2 furnished an intermediate cyclic allylsilane. Subsequently, TMSOTf promoted a [4 + 2]-annulation through trapping of an oxonium, generated by condensation between an aldehyde and the TBS protected alcohol resulted in the formation of a cis-fused hydroisochromene 13.

PubMed Disclaimer

Figures

Figure 1
Figure 1
Proposed tandem Diels–Alder/annulation sequence.
Scheme 1
Scheme 1. Preparation of Silicon-Substituted Diene 1
Scheme 2
Scheme 2. One-Pot Diels–Alder-Annulation Sequence with Various Aldehydes (4b–4g)
Isolated yield after purification by SiO2 chromatography.
Figure 2
Figure 2
Proposed transition state of [4 + 2]-annulations.
See this image and copyright information in PMC

Similar articles

See all similar articles

Cited by

References

    1. For ventiloquinones, see:

    2. Hanumaiah T.; Marshall D. S.; Rao B. K.; Rao C. P.; Rao G. S. R.; Rao J. U. M.; Rao K. V. L; Thomson R. H. Phytochemistry 1985, 24, 2373–2378.
    3. Jammula S. R.; Papalla S. B.; Telikepalli H.; Rao K. V. J.; Thomson R. H. Phytochemistry 1991, 30, 3741–3744.
    4. Ali S.; Read R. W.; Sotheeswaran S. Phytochemistry 1994, 35, 1029–1032.
    5. Brimble M. A.; Dancalf L. J.; Nairn M. R. Nat. Prod. Rep. 1999, 16, 267–281. - PubMed

    6. For other examples of natural products and bioactive molecules, see

    7. Hayashi T.; Smith F. T.; Lee K.-H. J. Med. Chem. 1987, 30, 2005–2008. - PubMed
    8. Abas F.; Lajis N. H.; Shaari K.; Israf D. A.; Stanslas J.; Yusuf U. K.; Raof S. M. J. Nat. Prod. 2005, 68, 1090–1093. - PubMed
    9. Shishido Y.; Wakabayashi H.; Koike H.; Ueno N.; Nukui S.; Yamagishi T.; Murata Y.; Naganeo F.; Mizutani M.; Shimada K.; Fujiwara Y.; Sakakibara A.; Suga O.; Kusano R.; Ueda S.; Kanai Y.; Tsuchiya M.; Satake K. Bioorg. Med. Chem. 2008, 16, 7193–7205. - PubMed
    10. Kuo Y.-J.; Hsiao P.-C.; Zhang L.-J.; Wu M.-D.; Liang Y.-H.; Ho H.-O.; Kuo Y.-H. J. Nat. Prod. 2009, 72, 1097–1101. - PubMed
    1. Butin A. V.; Abaev V. T.; Mel’chin V. V.; Dmitriev A. S. Tetrahedron Lett. 2005, 46, 8439–8441.
    2. Villeneuve K.; Tam W. Eur. J. Org. Chem. 2006, 5449–5453.
    3. Obika S.; Kono H.; Yasui Y.; Yanada R.; Takemoto Y. J. Org. Chem. 2007, 72, 4462–4468. - PubMed
    4. Morimoto K.; Hirano K.; Satoh T.; Miura M. J. Org. Chem. 2011, 76, 9548–9551. - PubMed
    5. Murai M.; Uenishi J.; Uemura M. Org. Lett. 2010, 12, 4788–4791. - PubMed
    6. Murai M.; Sota Y.; Onohara Y.; Uenishi J.; Uemura M. J. Org. Chem. 2013, 78, 10986–10995. - PubMed
    7. Malhotra D.; Liu L.-P.; Mashuta M. S.; Hammond G. B. Chem.—Eur. J. 2013, 19, 4043–4050. - PubMed
    8. Saito K.; Kajiwara Y.; Akiyama T. Angew. Chem., Int. Ed. 2013, 52, 13284–13288. - PubMed
    9. Cui Y.; Villafane L. A.; Clausen D. J.; Floreancig P. E. Tetrahedron 2013, 69, 7618–7626. - PMC - PubMed
    1. Yadav J. S.; Reddy B. V. S.; Ganesh A. V.; Kumar G. G. K. S. N. Tetrahedron Lett. 2010, 51, 2963–2966.
    2. Reddy B. V. S.; Borkar P.; Yadav J. S.; Sridhar B.; Grée R. J. Org. Chem. 2011, 76, 7677–7690. - PubMed
    3. Reddy B. V. S.; Kumar H.; Borkar P.; Yadav J. S.; Sridhar B. Eur. J. Org. Chem. 2013, 1993–1999.
    1. Wu J.; Pu Y.; Panek J. S. J. Am. Chem. Soc. 2012, 134, 18440–18446. - PubMed
    1. Huang H.; Panek J. S. J. Am. Chem. Soc. 2000, 122, 9836–9837.
    2. Lowe J. T.; Panek J. S. Org. Lett. 2005, 7, 3231–3234. - PubMed

Publication types

LinkOut - more resources