Enantioselective synthesis of natural polyoxygenated cyclohexanes and cyclohexenes from [(p-tolylsulfinyl)methyl]-p-quinols.

  title={Enantioselective synthesis of natural polyoxygenated cyclohexanes and cyclohexenes from [(p-tolylsulfinyl)methyl]-p-quinols.},
  author={M. Carmen Carre{\~n}o and Est{\'i}baliz Merino and Mar{\'i}a Ribagorda and {\'A}lvaro Somoza and Antonio Urbano},
  volume={13 4},
Exploitation of the beta-hydroxysulfoxide fragment present in a number of enantiomerically pure (SR)- and (SS)-[(p-tolylsulfinyl)methyl]-p-quinols allowed chemo- and stereocontrolled conjugate additions of different organoaluminium reagents to the cyclohexadienone moiety. The same fragment was also shown to act as an efficient chiral masking carbonyl group, after oxidation to sulfone and retroaddition in basic medium, with elimination of methyl p-tolyl sulfone. Through the use of both… 
Synthesis of 4-aminotropones from [(sulfinyl or sulfonyl)methyl]-substituted p-quinamines.
The introduction of a proline substituent in the nitrogen of the starting p-quinamine allowed the synthesis of an enantiopure 4-aminotropone, the asymmetric Diels-Alder reactions of which with maleimide occurred in a highly endo and pi-facial diastereoselective manner.
Towards configurationally stable [4]helicenes: enantioselective synthesis of 12-substituted 7,8-dihydro[4]helicene quinones.
Evidence is provided that, in addition to steric effects, a small but significant role of electronic effects is governing the configurational stability of such helical quinones.
Reactions of p‐Quinols with Aldehydes and Imines: Stereoselective Access to Polyheterobicyclic and Tricyclic Systems
Dihydrobenzo[1,3]dioxolanones, tetrahydrobenzo[d]oxazolones and heterotricyclic derivatives have been stereoselectively synthesized from p-quinols upon reaction with aldehydes or benzaldimines under
A Stereoselective Approach to Functionalized Cyclohexenones
A catalytic enantioselective approach to 4-hydroxy-6-methylcyclohex-2-enones is presented herein. The stereogenic information is generated through a copper-catalyzed 1,4-addition to p-benzoquinone
Divergent Approach to Gabosines and Anhydrogabosines: Enantioselective Syntheses of (+)‐Epiepoformin, (+)‐EpoKformin, (+)‐Gabosine A, and Gabosines B and F
A divergent approach to polyoxygenated methylcyclohexanes has been applied to synthesize several gabosines and anhydrogabosines. The starting hydroxycyclohexenone, which is readily available in any
Asymmetric Total Syntheses of (-)-Hedycoropyrans A and B.
The first and asymmetric total synthesis of (-)-hedycoropyrans A and B was accomplished in 18 steps with 5.4% overall yield, which might suggest the biogenetic origin of hedyCoropyran B.
Synthesis of Gabosine A and N from Ribose by the Use of Ring‐Closing Metathesis
A concise synthetic route is described for the synthesis of gabosine A and N. The key step uses a zinc-mediated tandem reaction where methyl 5-deoxy-5-iodo-2,3-O-isopropylidene-β-D-ribofuranoside is
A divergent strategy to synthesize gabosines featuring a switchable two-way aldol cyclization.
A new diversity-oriented approach for the gabosine-type carbasugars based on a tunable regioselective aldol cyclization of flexible precursor 2 is explored.
Friedel-Crafts Alkylation of Indoles with p-Quinols: The Role of Hydrogen Bonding of Water for the Desymmetrization of the Cyclohexadienone System.
Experimental results and theoretical calculations explained the enantioselectivity based on a transition state where two water molecules act as a tether joining the p-quinol with the phosphoric acid and the NH of indole, thus facilitating the desymmetrization of the prochiral cyclohexadienone framework.


The first synthesis of (-)-asperpentyn and efficient syntheses of (+)-harveynone, (+)-epiepoformin and (-)-theobroxide.
The enantioselective syntheses of (-)-theobroxide, a polyoxygenated cyclohexane natural compound with potent growth inducing properties in potato microtubers has been achieved via a 1,2 O-silyl migration between trans-hydroxyl groups and a remote hydroxyl directed epoxidation of an enone derived from quinic acid.
Studies of Diastereoselectivity in Conjugate Addition of Organoaluminum Reagents to (R)-[(p-Tolylsulfinyl)methyl]quinols and Derivatives
(R)-4-Hydroxy-4-[(p-tolylsulfinyl)methyl]-2,5-cyclohexadienones 1−3, and 6 reacted with organoaluminum derivatives from the pro-R conjugated position in a highly π-facial diastereoselective manner
Enantioselective synthesis and absolute configuration assignment of gabosine O. Synthesis of (+)- and (-)-gabosine N and (+)- and (-)-epigabosines N and O.
A rational approach to the synthesis of gabosines and other related carba-sugars starting from a masked p-benzoquinone has been designed and the absolute configuration of natural gabOSine O has been established.
Enantioselective synthesis of (+)- and (-)-dihydroepiepoformin and (+)-epiepoformin.
Key features include the stereocontrolled conjugate addition of AlMe3 to p-quinol 3 and retrocondensation to the ketone functionality, previous to oxidation of the beta-hydroxy sulfoxide moiety of advanced intermediates to the corresponding sulfone.
Conjugate additions of Me2CuLi to enantiopure γ-hydroxy-δ-sulfinyl and sulfonyl pentenoates
: [reaction: see text] A systematic study of dimethyl cuprate conjugate additions to diastereoisomeric ethyl gamma-hydroxy (or tert-butyldimethylsilyloxy)-delta-p-tolylsulfinyl-2-pentenoates and the
Total stereoselective synthesis of (+)-goniothalesdiol.
The key features were a completely diastereoselective reduction of a beta-ketosulfoxide to generate the stereogenic center at C-5 in 7 and formation of the 2,5-cis-substituted tetrahydrofuran ring in 10 from a stereoselectives Et(3)SiH/TMSOTf-promoted reductive cyclization/deoxygenation.