A one-step highly stereocontrolled synthesis of (–)- and (+)-hexahydrocannabinol and related compounds

Casiraghi, Giovanni; Cornia, Mara; Casnati, Giuseppe; Fava, Giovanna Gasparri; Belicchi, Marisa Ferrari

doi:10.1039/c39860000271

Cited by 30 publications

(36 citation statements)

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“…Refluxing the latter in dichlorobenzene gave the same compound, 12a. The optical rotation of 12a is consistent with other HHC analogs (18). The stereochemistry of 12a was confirmed with NMR experiments and references to the analysis of similar compounds described elsewhere (34)(35)(36).…”

Section: Synthesis Of Cannabinoidssupporting

confidence: 80%

“…The nOe experiments (data not given) confirm these assignments and show H-lOa clearly to be a doubleted triplet, as expected. Finally, 1 3 c NMR spectral analysis was consistent with the given structure (18).…”

Section: Synthesis Of Cannabinoidsmentioning

confidence: 57%

“…Stereocontrolled syntheses of enantiomeric pure (+)-and (-)-hexahydrocannabinols (HHC) and analogs via intramolecular Diels-Alder reactions of orthoquinone methide have previously been rpeorted (2,13,(15)(16)(17)(18). Using the normal procedure to prepare 2-phenyl-4H-1,3,2-benzodioxaborins, reaction of 3-methoxyphenol with (R)-(+)-citronela12 gave a 70% isolated yield of the o ti 2 P :…”

Section: Synthesis Of Cannabinoidsmentioning

confidence: 99%

“…However, in the presence of electron-rich dienophiles they often react preferentially with these species to form potentially complex chromans (7-1 1). Intramolecular trapping of these quinone methides by otherwise unreactive dienophiles has also been documented (12)(13)(14)(15)(16)(17)(18). In the presence of nucleophiles, ortho-quinone methides generated in situ undergo Michael addition to give ortho-substituted phenols (5,17,19).…”

Section: Introductionmentioning

confidence: 97%

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Reactions of 2-phenyl-4H-1,3,2-benzodioxaborin, a stable ortho-quinone methide precursor

Chambers¹,

Crawford²,

Williams³

et al. 1992

Can. J. Chem.

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Thermolysis of 1-phenyl-4H-1,3,2-benzodioxaborins generated the corresponding ortho-quinone methides, which were found to undergo intermolecular cycloaddition reactions with ethyl vinyl ether, dihydropyran, p-methylstyrene, cyclohexene, and 1-ethoxy-1-z-trimethylsiloxy-1-propenes to give various substituted chromans. Intramolecular trapping of the quinone methides with an olefin led to the syntheses of several analogs of tetrahydrocannabinols. ortho-Quinone methides, generated by treatment of the 2-phenyl-4H-1,3,2-benzodioxaborins with a Lewis acid, react with various nucleophiles to give the corresponding 1,4-addition products. Thus, alkyl and aryl thiols, alcohols, amine, hydride, ally1 trimethylsilane, acetophenone, and diethylmalonate as well as some aryl compounds react with the quinone methide to give various 2-substituted phenols. Intramolecular reaction of the quinone methide with an aryl group led to the preparation of some 4-phenylchromans and tetralins. La thermolyse des 2-phknyl-4H-1,3,2-benzodioxaborines conduit aux ortho-quinomkthanes correspondantes qui subissent des rkactions de cycloaddition interrnolkculaires avec l'ethoxykthkne, le dihydropyrane, le p-mkthylstyrkne, le cyclohexkne et les 1 -6thoxy-1 -z-trimkthylsiloxyprop-1 -knes pour conduire a divers chromanes substituks. Le pikgeage intrarnolkculaire des quinomkthanes avec une olefine permet la synthkse de plusieurs analogues des tktrahydrocannabinols. Les ortho-quinomkthanes, prCparCs par traitement des 2-phknyl-4H-1,3,2-benzodioxaborines avec un acide de Lewis, rkagissent avec divers nuclkophiles pour donner les produits d'additions-1,4 correspondants. Ainsi, les alkyl-et aryl-thiols, les alcools, les amines, les hydrures, l'allyltrim~thylsilane, I'acCtophknone et le malonate d'kthyle ainsi que certains composks aromatiques rkagissent avec le quinomkthane pour conduire a divers phknols substituks en position 2. La reaction intramolCculaire des quinomkthanes avec un groupe aryle conduit a la prkparation de quelques 4-phknylchromanes et de tktralines.[Traduit par la rkdaction]

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Section: Synthesis Of Cannabinoidssupporting

confidence: 80%

Section: Synthesis Of Cannabinoidsmentioning

confidence: 57%

Section: Synthesis Of Cannabinoidsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 97%

See 2 more Smart Citations

Reactions of 2-phenyl-4H-1,3,2-benzodioxaborin, a stable ortho-quinone methide precursor

Chambers¹,

Crawford²,

Williams³

et al. 1992

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…From a Cambridge Structural Database search (Groom et al, 2016), we found compounds identified by refcodes OKEYUB (Xiao et al, 2021), QABVEY (Wang et al, 2021), ALTENU (McPhail et al, 1973), AMUYIS (Alzaydi et al, 2016), ANOVEG (Sosnovskikh et al, 2016), ANOVIK (Sosnovskikh et al, 2016), BUWJEK (Parveen et al, 2015), BUXLOW (Fatunsin et al, 2010), DIPTUR (Casiraghi et al, 1986), DISJAS (Lee et al, 2013), SEDFEN (Appel et al, 2006), SIVQIZ (Poudel & Lee, 2014), SIJZER (Hussain et al, 2007), TUPJOE (Siegel et al, 2010), ZAQHIK (Dasari et al, 2012) and IZACIY (Duan et al, 2021) to be similar to the title compound.…”

Section: Structure Descriptionmentioning

confidence: 99%