Origins of the regioselectivities in the Diels-Alder reactions of vinylindenes with 1,4-quinone monoketal and acrolein dienophiles Journal Article
| Authors: | Hayden, A. E.; DeChancie, J.; George, A. H.; Dai, M.; Yu, M.; Danishefsky, S. J.; Houk, K. N. |
| Article Title: | Origins of the regioselectivities in the Diels-Alder reactions of vinylindenes with 1,4-quinone monoketal and acrolein dienophiles |
| Abstract: | (Chemical Equation Presented) Computations with density functional theory (B3LYP/6-31G(d)) have elucidated the origins of regioselectivities in the Diels-Alder reaction of vinylindene with a 1,4-quinone monoketal reaction that was employed as the key step in the synthesis of fluostatin C. Frontier Molecular Orbital theory and an electrostatic model are applied to the reactions of alkyl-substituted and vinylindene dienes with 1,4-quinone monoketal and acrolein dienophiles. Regiochemical results that deviate from expectation are explained by a progression from electronic to steric control upon the addition of a Lewis acid catalyst. © 2009 American Chemical Society. |
| Keywords: | unclassified drug; drug structure; drug synthesis; quinones; thermodynamics; molecular structure; catalysis; structure analysis; chemical reactions; static electricity; b3lyp/6-31g; chemical equations; diels-alder reaction; dienophiles; electrostatic models; frontier molecular orbitals; lewis acid catalysts; regiochemical; steric control; aldehydes; herbicides; molecular orbitals; olefins; density functional theory; acetal derivative; acrolein derivative; fluorenone derivative; fluostatin c; lewis acid; vinyl derivative; catalyst; diels alder reaction; reaction analysis; stereospecificity; acids; acrolein; chemistry, organic; fluorenes; indenes; models, chemical; molecular conformation; vinyl compounds |
| Journal Title: | Journal of Organic Chemistry |
| Volume: | 74 |
| Issue: | 17 |
| ISSN: | 0022-3263 |
| Publisher: | American Chemical Society |
| Date Published: | 2009-09-04 |
| Start Page: | 6770 |
| End Page: | 6776 |
| Language: | English |
| DOI: | 10.1021/jo901473h |
| PUBMED: | 19663431 |
| PROVIDER: | scopus |
| DOI/URL: | |
| Notes: | --- - "Cited By (since 1996): 5" - "Export Date: 30 November 2010" - "CODEN: JOCEA" - "Source: Scopus" |
