Synthesis and Refunctionalization of Hexahydro-naphthalenone Systems

Abstract

Cis-and trans-hexahydronaphthalenones 8 and 9 were readily obtained by Diels-Alder addition and epimerization. Highly stereoselective reduction of 9 furnished the alcohol 10, which could be converted to the epimeric alcohol 11 by Mitsunobu inversion. The propionate 13 derived from 11 failed to undergo a Claisen rearrangement.

Mitsunobu and Related Reactions: Advances and Applications

“…Due to the large number of other applications involving similar inversion/epimerization, we only list them here; the structural drawings pertaining to these references are given in the Supporting Information (Table S1). These pertain to the synthesis of (i) pregnanone derivatives, (ii) glucosphingolipids, (iii) pyrrolidine-amide oligonucleotide mimics, (iv) tubronic acid, (v) enantiopure butanoates, (vi) macroviracins, (vii) reduced products of cis - and trans -hexahydronaphthalenones, (viii) stereoinversion of myo -inositol into scyllo -inositol, (ix) orthogonally-protected and unprotected depsipeptides such as l -Lys- d -Ala- d -Lac and Boc-( S )-HOMeVal-( R )-Hmb, (x) (2 S ,3 S ,4 R )-4-( tert -butyldimethylsilyloxy)-2,3-isopropylidenedioxy-4-phenylbutanoate, (xi) dihydroxycholesterol, (xii) the acetate of the triol derived from jasminine, (xiii) stereochemically inverted products of xylofuranosyl derivatives, (xiv) 6- epi- aucubin, (xv) hydroxyethylene dipeptide isosteres (e.g. L-682,679), (xvi) orobanchol (a germination stimulant), (xvii) long chain pentadeca-1,3,5,7,9,11,13,15-octols (16 diastereomers), (xviii) mycalamide A (natural product), (xix) murisolin (natural product), (xx) leucascandrolide A (natural product with a sterically congested carbon), , (xxi) l -lyxose esters, (xxii) cryptophycin (5-hydroxy acid subunit), (xxiii) polycyclic carbohydrates, (xxiv) protected aminooxyprolines, (xxv) carbahexopyranose stereoisomers, (xxvi) deoxynucleic guanidine (DNG) oligonucleotide, (xxvii) D-hica, a component of kulokekahilide-2, (xxviii) methylsulfonate esters, (xxix) (4 R ,5 S )- and (4 S ,5 R )-muricatacins, (xxx) trioxilins, (xxxi) functionalized β-C-glycosyl aldehydes (a part of ambruticin), (xxxii) pyrrolidinols, (xxxiii) carbocyclic nucleosides, (xxxiv) Δ 2 -OPC-8:0 (a substituted cyclopentanone derivative), (xxxv) fluorescence-labeled probes based on phyllanthurinolactone [in these cases, 4-dimethylaminophenyldiphenylphosphine ( 2 ) instead of Ph 3 P worked better], (xxxvi) (+)-cardiobutanolide, (xxxvii) 3-amino-2,3,6-trideoxysugars, (xxxviii) sesquiterpene lactones, (xxxix) 3-methylcyclopentadecanol, (xl) optically active β-methyl-γ-alkyl-γ-butyrolactone, (xli) chiral P,N-ligands with a cyclohexane backbone, (xlii) optically active aminobenzindanol, (xliii) cyclopenta[ d ]pyridazinediol, (xliv) 4-hydroxytetrahydropyranone, (xlv) alkynic esters as precurso...…”

“…135 Due to the large number of other applications involving similar inversion/epimerization, we only list them here; the structural drawings pertaining to these references are given in the Supporting Information (Table S1). These pertain to the synthesis of (i) pregnanone derivatives, 153 (ii) glucosphingolipids, 154 (iii) pyrrolidine-amide oligonucleotide mimics, 155 (iv) tubronic acid, 156 (v) enantiopure butanoates, 157 (vi) macroviracins, 158 (vii) reduced products of cis-and transhexahydronaphthalenones, 159 (viii) stereoinversion of myoinositol into scyllo-inositol, 160 (ix) orthogonally-protected and unprotected depsipeptides such as L-Lys-D-Ala-D-Lac 161 and Boc-(S)-HOMeVal-(R)-Hmb, 162 (x) (2S,3S,4R)-4-(tert-butyldimethylsilyloxy)-2,3-isopropylidenedioxy-4-phenylbutanoate, 163 (xi) dihydroxycholesterol, 164 (xii) the acetate of the triol derived from jasminine, 165 (xiii) stereochemically inverted products of xylofuranosyl derivatives, 166 (xiv) 6-epiaucubin, 167 (xv) hydroxyethylene dipeptide isosteres (e.g. L-682,679), 168 (xvi) orobanchol (a germination stimulant), 169 (xvii) long chain pentadeca-1,3,5,7,9,11,13,15-octols (16 diastereomers), 170 (xviii) mycalamide A (natural product), 171 (xix) murisolin (natural product), 172 (xx) leucascandrolide A (natural product with a sterically congested carbon), 173,174 (xxi) L-lyxose esters, 175 (xxii) cryptophycin (5-hydroxy acid subunit), 176 (xxiii) polycyclic carbohydrates, 177 (xxiv) protected aminooxyprolines, 178 (xxv) carbahexopyranose stereoisomers, 179 (xxvi) deoxynucleic guanidine (DNG) oligonucleotide, 180 (xxvii) D-hica, a component of kulokekahilide-2, 181 (xxviii) methylsulfonate esters, 182 (xxix) (4R,5S)-and (4S,5R)-muricatacins, 183 (xxx) trioxilins,…”