20484-80-4Relevant academic research and scientific papers
Regio- and stereochemistry of Michael addition of methanol to Thiele's ester
Minter, David E.,Smith, William B.,Marchand, Alan P.,Etukala, Jagan Reddy,Sivappa, Rasapalli
, p. 174 - 179 (2004)
Acid-promoted esterification of Thiele's acid with methanol was found to afford three products. In addition to the expected major product (i.e. the corresponding dimethyl ester, 2a), two minor products are obtained, one of which, 3, results from subsequen
Prying open a Thiele cage: Discovery of an unprecedented extended pinacol rearrangement
Dao, Nathan,Sader, Jonathan K.,Oliver, Allen G.,Wulff, Jeremy E.
, p. 1600 - 1603 (2019/02/07)
The first extended pinacol rearrangement across an sp3-sp3 bond is reported. The reaction appears to be both stereo- and regio-specific, and results in an extremely rare example of cage opening for a 1,3-bishomocubane structure deriv
Resolution of Thiele's acid
Chen, Jun,Sun, Xuxin,Oliver, Allen G.,Wulff, Jeremy E.
, p. 234 - 238 (2017/03/09)
Thiele's acid has been resolved for the first time by diastereomeric salt formation with brucine. Determination of absolute stereochemistry was accomplished by X-ray crystallography of the corresponding diester. We anticipate that access to optically resolved Thiele's acid will stimulate its use in a diverse range of applications requiring chiral molecular clefts.
Expansion of Thieles Acid Chemistry in Pursuit of a Suite of Conformationally Constrained Scaffolds
Chen, Jun,Kilpatrick, Brenden,Oliver, Allen G.,Wulff, Jeremy E.
, p. 8979 - 8989 (2015/09/28)
The Diels-Alder dimer of cyclopentadiene carboxylate, Thieles acid has conformational properties that make it attractive as a molecular scaffold for applications in supramolecular and biological chemistry. However, a lack of known reaction methodology for derivatives of Thieles acid (or the corresponding esters) has hampered its utilization in these fields. We describe an improved preparation of Thieles esters and survey the chemistry of these versatile intermediates. As part of this effort, we also describe the synthesis of a suite of Thieles acid (or ester) analogues spanning a broad range of cleft angles.
Thiele's acid revisited: Isolation and characterization of two minor products formed by carbonation of cyclopentadienide anion
Marchand, Alan P.,Namboothiri,Lewis, Scott B.,Watson, William H.,Krawiec, Mariusz
, p. 12691 - 12698 (2007/10/03)
Carbonation of sodium cyclopentadienide leads to the formation of 3aα,4α,7α.7aα-tetrahydro-4,7-methano-1H-indene-2,6-dicarboxylic acid [i.e., 'Thiele's acid', 2i (R = H), 60%] along with several isomeric C12H12O4 minor products. The dimethyl esters of two of these minor products, i.e., dimethyl 3aα,4α,7α,7aα-tetrahydro-4,7-methano-1H-indene- 2,4-dicarboxylate [2a (R = Me), 13%) and the corresponding 3a,6- dicarboxylate [2n (R = Me), 1%] have been isolated and characterized. Intramolecular [2 + 2] photocyclization of 2a (R = Me) afforded 3a (R = Me) (30%), whose structure was established unequivocally by application of X-ray crystallographic techniques.
