Bridged aromatic alkenes for the study of carbocation–π interaction

Spencer, Thomas A.; Popovici‐Muller, Janeta; Beusichem, Bobbijo van; MacMillan, Celeste Viscardi; Lavey, Carolee; Sin, Jessica M.; Ditchfield, R.

doi:10.1016/j.tet.2010.04.029

Cited by 12 publications

(6 citation statements)

References 59 publications

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“…Eventually, oxidation to the desired methylketone was realized by a stepwise transformation. Thus, compound 12 underwent Lemieux‐Johnson oxidation [13] to give aldehyde 13 , which was subjected to TMS‐diazomethane in the presence of MgBr 2 involving hydride migration to construct the methylketone moiety [14] . Finally, demethylation via quinone formation completed the total synthesis of lucidumone [15] ( 1 ; racemic).…”

Section: Methodsmentioning

confidence: 99%

Total Synthesis of Lucidumone through Convenient One‐pot Preparation of the Tetracyclic Skeleton by Claisen Rearrangement and Subsequent Intramolecular Aldol Reaction

et al. 2023

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The total synthesis of lucidumone (1), a Ganoderma meroterpenoid, was accomplished in racemic form from easily prepared 6 and 7 in 10 steps as the longest linear sequence. The synthesis was completed through one-pot preparation of the tetracyclic core skeleton by Claisen rearrangement followed by an intramolecular aldol reaction. The intramolecular aldol reaction allowed for the stereocontrolled construction of the bicyclo [2.2.2] octane skeleton fused to an indanone structure. The enantioselective total synthesis of 1 was also described via a chiral transfer strategy in the Claisen rearrangement.

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Section: Methodsmentioning

confidence: 99%

Total Synthesis of Lucidumone through Convenient One‐pot Preparation of the Tetracyclic Skeleton by Claisen Rearrangement and Subsequent Intramolecular Aldol Reaction

et al. 2023

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“…In this field, some important new developments have been realized starting from five-membered ring precursors since the pioneering work from Lansbury’s group in 1966 . Very recently, Spencer et al used this robust procedure to prepare the benzobicyclo[3.2.1]octenes 110a , b as model substrates to study carbocation−π interactions in these strained systems (Scheme ) . The desired ketone 109 was obtained in 64% yield from chlorovinyl indene 108 by simple treatment with formic acid and further converted to the required stereodefined alkenes 110a , b .…”

Section: Bicylo[321] Ring System From Five-membered Ringsmentioning

confidence: 99%

Syntheses and Applications of Functionalized Bicyclo[3.2.1]octanes: Thirteen Years of Progress

2012

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“…This structure was stabilized by a CH···π hydrogen bond. Recently, a suggestion has been made (supported by calculations at the M06/cc-pVTZ level of theory) that the intramolecular interaction of the carbocationic center with an aromatic ring in the protonated benzobicyclo[3.2.1]octene, benzobicyclo[2.2.1]heptene, and benzobicyclo[4.2.1]nonene will belong, by steric reasons, solely to the η 1 π rather than to the σ type (see A in Scheme ). It is significant that the EC ipso C para angle (α) is of key importance for assigning the complexes of electrophiles (in particular, R 3 C + and R 3 Si + ) with arenes to a certain type , (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Cage Complexes of Carbenium and Silylium Cations with an Aromatic Base. Is the η⁶Coordination Type Realizable?

2012

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The cage cations [E((CH2)3)3C6R3]+ (E = C (1), Si (2); R = H (a), Li (b), F (c)) were studied theoretically using the MP2/6-311++G(d,p) approach. The migration of the electrophilic center E and a proton around the perimeter of the arene ring in the cations [E((CH2)3)3C6H3]+ was considered. Our results are indicative of the π type of E←arene coordination in the intramolecular complexes [E((CH2)3)3C6R3]+. The cation [Si((CH2)3)3C6H3]+ (2a), which corresponds to a peak (M – CH3)+ at m/z 229 in the mass spectrum of methylsilacyclophane, exists in a firmly established η1π form, as opposed to the case for the known complexes of the trivalent silicon atom with aromatic bases. The species [C((CH2)3)3C6F3]+ (1c), as well as 4a, obtained by connecting the equatorial carbon atoms in [Si((CH2)3)3C6H3]+ by a methylene bridge, are the first representatives of stable “face” complexes of carbenium and silylium cations with a benzene ring. The process of deprotonation of the complexes [C((CH2)3)3C6H3]+, [Si((CH2)3)3C6H3]+, and 4a was found to be energetically unfavorable, even in the presence of a strong base such as NEt3. The effect of the counterions BX4 – (X = F, C6F5) and the polarity of solvents on the structure of the above cations was investigated using the examples of toluene and DMSO.

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Bridged aromatic alkenes for the study of carbocation–π interaction

Cited by 12 publications

References 59 publications

Total Synthesis of Lucidumone through Convenient One‐pot Preparation of the Tetracyclic Skeleton by Claisen Rearrangement and Subsequent Intramolecular Aldol Reaction

Total Synthesis of Lucidumone through Convenient One‐pot Preparation of the Tetracyclic Skeleton by Claisen Rearrangement and Subsequent Intramolecular Aldol Reaction

Syntheses and Applications of Functionalized Bicyclo[3.2.1]octanes: Thirteen Years of Progress

Cage Complexes of Carbenium and Silylium Cations with an Aromatic Base. Is the η⁶Coordination Type Realizable?

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Bridged aromatic alkenes for the study of carbocation–π interaction

Cited by 12 publications

References 59 publications

Total Synthesis of Lucidumone through Convenient One‐pot Preparation of the Tetracyclic Skeleton by Claisen Rearrangement and Subsequent Intramolecular Aldol Reaction

Total Synthesis of Lucidumone through Convenient One‐pot Preparation of the Tetracyclic Skeleton by Claisen Rearrangement and Subsequent Intramolecular Aldol Reaction

Syntheses and Applications of Functionalized Bicyclo[3.2.1]octanes: Thirteen Years of Progress

Cage Complexes of Carbenium and Silylium Cations with an Aromatic Base. Is the η6Coordination Type Realizable?

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Cage Complexes of Carbenium and Silylium Cations with an Aromatic Base. Is the η⁶Coordination Type Realizable?