Tricyclo[3.2.1.03,6]octan-7-yl derivatives. Synthesis, chemistry, and solvolytic studies

Monti, Stephen A.; Yuan, Sun-Shine

doi:10.1021/jo00821a018

Cited by 13 publications

(10 citation statements)

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“…The organic phase was dried (MgS04) and filtered through neutral aluminum oxide (50 g, activity 111) using methylene chloride (700 mL). After concentration at reduced pressure, the solid residue was crystallized from benzene to give 6.0 g (73%) of 16c: mp 130-1 32 OC;IR(KBr) 1730cm-I;NMR(CDCI3)6 1.12(d,3,J= 7Hz), 1.62 (s, 3), 1.6-2.6, 2.10 (m, s, 9), 3.07 (s, 3) …”

Section: 7-dimethyl-exo-4-hydroxy-exo-3-methanesulfonatobicyclo-[3mentioning

confidence: 99%

“…As outlined in 2lb, the trimethylsilyl keto mesylate 18 (2.78 g, 6.9 mmol) in benzene (75 mL) was allowed to react with a solution of potassium (7.0 g, 0.051 g-atom) in 2-methyl-2-butanol (75 mL) for 20 h at room temperature. Distillation of the crude residue gave 1.98 g (94%) of pure 22 bp I 15-120 "C (0.1 mm); IR (CC14) 1765,1260,1250,1170,1120, 1045 cm-I; N M R (CDCI3) 6 0.18 (s, 9), 1.20 (s, 3), 1.66 (d, 6, J = 7 Hz), 1.0-2.8 (m, 1 I), and 5.15 ppm (m, 1); mass spectrum m/e (re1 intensity) 264 (4), 143 (98), 73 (100).…”

Section: 6-dimethyl-exo-2-trimethylsiloxytricyclo[32103~6]octan-mentioning

confidence: 99%

“…A solution of LiAIH4 (50 mg,13 mmol) in ether (8 mL) was added to a stirred solution of tricyclic ketone 2lb (208 mg, 8.7 mmol) in ether ( I O mL) at 0 "C. After 20 min ethyl acetate (1 .O g) was added followed by a cold saturated sodium potassium tartrate solution (50 mL). The mixture was extracted with ether and the combined extracts were washed with brine, dried (MgSOd), and evaporated under reduced pressure to give 205 mg (97%) of the crude alcohol 27a: IR (CC14) 3600 cm-I; NMR (CDCI3) 6 0.14 (s, 9), 1.28 (s, 3), 1.57 (s, 3), 1. 5-2.3 (m, 7), 2.38 (s, l), and 3.76 ppm (m, 1).…”

Section: B a Solution Of 2lb (326 Mg 136 Mmol) In T H F (3 Ml) Wasmentioning

confidence: 99%

“…Using the procedure described for 29a, tricyclic ketone 22 (400 mg, 1.3 mmol) yielded a residue that was purified by chromatography on silica gel (20 g) using ether, and then crystallized from hexane to give 241 mg (79%) of 29b: mp 103-104 "C; IR (CH2C12) 3395, 1680, 1590 cm-I; NMR (CDC13) 6 1.26 (d, I , J = 8 Hz), 1. 5-2.0 (m, 9), 1.8-3.0 (m, 9), and 4.9-6.0 ppm (m, 4); mass spectrum m/e (re1 intensity) 164 (loo), 119 (52) endo-6-Cyano-2-methyI-6-(4-methylpent-3-en-l-yl)bicy~lo-[3.l.lpept-2-ene (30b). Using the procedure described for 30a, bicyclic amide 29b (210 mg, 0.9 mmol) furnished 153 mg (79%) of liquid 30b IR (CC14) 2230 cm-l; NMR (CDC13) 6 1.40 (d, 1, J = 8 Hz), 1.6-2.0 (m, 9), 1.85-2.9 (m, 9), and 4.9-5.6 ppm (m, 2).…”

Section: Endo-6-carbamoyl-26-dimethyibicyclo[3ll]hept-2-ene (29a)mentioning

confidence: 99%

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Total synthesis of racemic .alpha.-trans- and .alpha.-cis-bergamotene and .alpha.-pinene

Larsen¹,

Monti²

1977

J. Am. Chem. Soc.

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The stereoselective total synthesis of racemic a-trans-(1) and of racemic a-cis-(2) bergamotene and the direct preparation of racemic a-pinene (3) from 4-methylbicyclo[3.2. IIoct-3-en-6-one (14) are described. The key steps involve formation of the cyclobutane ring by intramolecular ring closure of the bicyclic precursors 16d and 18 and sodium amide initiated fragmentation of the 8-trimethylsilyloxy ketone moiety of the resulting tricyclic derivatives 21b and 22 to give the required 2-methylbicyclo[3.1. I ] hept-2-ene skeletons 29 which contain stereocontrolled, differentiated functionality at the quaternary C-6 center. Functional group modification of 29 then completes the fully stereocontrolled, total synthesis of these natural substances.The mono-and sesquiterpenes comprising the pinane family of natural products are characterized structurally by the presence of a bicyclo[3.1. ]]heptane nucleus. The widely distributed essential oil hydrocarbon a-trans-bergamotene2 (1) and its cis isomer3 (2) are representative of the known sesquiterpenes: while the ubiquitous a-pinene (3) and the highly oxygenated paeoniflorin5 (4) are illustrative of the structural c6H5c02B Gluo I ~~= a i~~(~~( -c ( a i~)~, at^ 4 2 R1=M3, R z = O~& H~~I -C C M~)~ 3 R1=R2=043variety found in the monoterpene members of this family. Previous synthetic efforts have resulted in the preparation of the three a hydrocarbons 2,' and 3,8a*c although the fundamental synthetic objectives presented by these substances, (1) the direct construction of the acid-labile 2-methylbicyclo[3.1 .l]hept-2-ene skeleton and (2) the unambiguous stereocontrol of the quaternary C-6 carbon center, have only been partially achieved by these earlier endeavors.Three basic routes have been used to prepare the symmetrically substituted 6,6-dimethylbicyclo[ 3.1. I] heptane nucleus: formation of the three-carbon bridge by ring closure of a cyclobutane substrate;8a,b preparation of the one-carbon bridge by intramolecular alkylation of a cyclohexanone derivative;8c and intramolecular photochemical [2 + 21 cycloaddition of an acyclic precursor.8d Of these, a photochemical [2 + 21 cycloaddition was employed as the key step in the synthesis of a-trans-bergamotene (1) to prepare a mixture of C-5 isomers 5 (5:3) in which the desired trans isomer predominated (eq trans/cis = 5 : 3 5

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Section: 7-dimethyl-exo-4-hydroxy-exo-3-methanesulfonatobicyclo-[3mentioning

confidence: 99%

Section: 6-dimethyl-exo-2-trimethylsiloxytricyclo[32103~6]octan-mentioning

confidence: 99%

Section: B a Solution Of 2lb (326 Mg 136 Mmol) In T H F (3 Ml) Wasmentioning

confidence: 99%

Section: Endo-6-carbamoyl-26-dimethyibicyclo[3ll]hept-2-ene (29a)mentioning

confidence: 99%

See 2 more Smart Citations

Total synthesis of racemic .alpha.-trans- and .alpha.-cis-bergamotene and .alpha.-pinene

Larsen¹,

Monti²

1977

J. Am. Chem. Soc.

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“…(7), HÀC(7')); 1.66 (dm, J 8.55, 2 H, HÀC(7), HÀC(7')); 1.65 (dd, J 12.30, 3.71, 2 H, HÀC(6), HÀC(6')); 1.12 (dd, J 12.30, 2.66, 2 H, HÀC(6), HÀC(6')). (31). Ozone was bubbled into a soln.…”

mentioning

confidence: 99%

Stereospecific Synthesis of Carbanucleotides Designed for Antisense Methodology.

2004

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A short stereospecific synthesis of the carbocyclic 2'-deoxynucleoside analogues 36 and 37 (Schemes 2 and 5) and 45 and 46 (Schemes 2 and 6) starting from optically active 8,9,10-trinorborn-5-en-2-one (1) is described. As two functional groups capable to react with each other are present in the same molecule of the synthetic carbanucleosides, the latter can form polymers similar to oligonucleotides.

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TheBaeyer–VilligerOxidation of Ketones and Aldehydes

1993

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The oxidative conversion of alicyclic ketones into lactones with permonosulfuric acid was discovered by Baeyer and Villiger in 1899, and in their honor the general process by which ketones are converted into esters or lactones is now known as the Baeyer–Villiger reaction. The literature on this synthetically useful process has been reviewed comprehensively through 1953 in Volume 9 of Organic Reactions , and less comprehensive reviews of the reaction have appeared since then. More recent investigations have led to the development of new synthetic reagents, to improvements in experimental reaction conditions, and to a better understanding of regiochemical and stereochemical aspects of the reaction. Baeyer–Villiger reactions now often can be carried out with functional group chemoselectivity and regiochemical control. Although the recent removal from commerce of 90% hydrogen peroxide and reagents based upon this oxidant are a setback to Baeyer–Villiger reaction methodology, alternative reagents, catalysts, and methods described in this review are available to fill the gaps. The definition of the Baeyer–Villiger reaction is somewhat fuzzy, and can be considered to include both ketones and aldehydes. In addition to the traditional use of organic and inorganic peracids as oxidants, examples of oxygen insertion reactions using hydrogen peroxide, alkyl peroxides, and several metal ion oxidants are considered to fall within the scope of this chapter and are included in the tabular survey.

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Tricyclo[3.2.1.03,6]octan-7-yl derivatives. Synthesis, chemistry, and solvolytic studies

Cited by 13 publications

References 0 publications

Total synthesis of racemic .alpha.-trans- and .alpha.-cis-bergamotene and .alpha.-pinene

Total synthesis of racemic .alpha.-trans- and .alpha.-cis-bergamotene and .alpha.-pinene

Stereospecific Synthesis of Carbanucleotides Designed for Antisense Methodology.

TheBaeyer–VilligerOxidation of Ketones and Aldehydes

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