An expedient synthesis of 6-Vinylfulvene

Erden, İhsan; Sabol, Jenny; Gubeladze, Ana; Ruiz, A Santos

doi:10.3906/kim-1302-74

Cited by 3 publications

(5 citation statements)

References 13 publications

(21 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To avoid this, they devised a one-pot synthesis of utilizing a sulfide oxidation and subsequent sulfoxide elimination strategy. 63 This protocol offers an excellent strategy for the synthesis of unsubstituted and substituted 6-vinylfulvene (Scheme 4).…”

Section: Extension Of Conventional Methodsmentioning

confidence: 97%

“…An exceptionally simple and efficient synthesis of 6-methyl-6-vinylfulvene 21 was developed by Erden and Gärtner (Scheme ). Later, the authors devised a convenient three-step protocol utilizing a sulfide oxidation and subsequent sulfoxide elimination strategy . This protocol offers an excellent strategy for the synthesis of unsubstituted and substituted 6-vinylfulvene (Scheme ).…”

Section: Synthesis Of Pentafulvenesmentioning

confidence: 99%

See 1 more Smart Citation

Recent Advances in the Chemistry of Pentafulvenes

et al. 2017

View full text Add to dashboard Cite

Pentafulvenes are a unique class of compounds that originally attracted attention due to their propensity to display nonbenzenoid aromaticity. Subsequently, they were recognized as valuable synthons for the construction of a wide range of compounds by virtue of their ability to display multiple cycloaddition profiles. Naturally, this area of organic chemistry has experienced rapid growth over the last five decades, fueled by elegant work showcasing the unique reactivity of pentafulvenes in a plethora of cycloaddition reactions. In this Review, we have attempted to provide a systematic account of the methods for the generation of pentafulvenes, their rich and varied cycloaddition chemistry, organometallic reactions, and theoretical studies that support their versatility. Further, we have highlighted their applications in the synthesis of a variety of complex structural frameworks. It is our conviction that this Review will be useful to a wide range of chemists, and will spur further research in this promising area.

show abstract

Section: Extension Of Conventional Methodsmentioning

confidence: 97%

Section: Synthesis Of Pentafulvenesmentioning

confidence: 99%

Recent Advances in the Chemistry of Pentafulvenes

et al. 2017

View full text Add to dashboard Cite

show abstract

“…Fulvenes constitute a fascinating class of cross-conjugated olefins, and since their first synthesis by Thiele in 1900 1 they have commanded considerable interest due their diverse reactivities. 2 Our own efforts in this area focused mainly on the development of new methods for their synthesis, 3 − 6 their cycloaddition chemistry, and in particular, their reactions with singlet oxygen. 7 − 11 In the course of our studies, we found that the fulvenyl unit exerts a considerable electron-withdrawing effect on alkyl, aryl, and vinyl groups attached to the exocyclic double bond (C6), though our findings have been qualitative to date.…”

Section: Introductionmentioning

confidence: 99%

Effect of Allylic Groups on S_N2 Reactivity

et al. 2014

View full text Add to dashboard Cite

The activating effects of the benzyl and allyl groups on SN2 reactivity are well-known. 6-Chloromethyl-6-methylfulvene, also a primary, allylic halide, reacts 30 times faster with KI/acetone than does benzyl chloride at room temperature. The latter result, as well as new experimental observations, suggests that the fulvenyl group is a particularly activating allylic group in SN2 reactions. Computational work on identity SN2 reactions, e.g., chloride– displacing chloride– and ammonia displacing ammonia, shows that negatively charged SN2 transition states (tss) are activated by allylic groups according to the Galabov–Allen–Wu electrostatic model but with the fulvenyl group especially effective at helping to delocalize negative charge due to some cyclopentadienide character in the transition state (ts). In contrast, the triafulvenyl group is deactivating. However, the positively charged SN2 transition states of the ammonia reactions are dramatically stabilized by the triafulvenyl group, which directly conjugates with a reaction center having SN1 character in the ts. Experiments and calculations on the acidities of a variety of allylic alcohols and carboxylic acids support the special nature of the fulvenyl group in stabilizing nearby negative charge and highlight the ability of fulvene species to dramatically alter the energetics of processes even in the absence of direct conjugation.

show abstract

“…The reported yield across the three steps was 37% including a purification after each step. 26 Kaiser and Hafner showed that 6-(2-aminovinyl)fulvenes would undergo a solution-phase thermal cyclisation and isomerisation in boiling piperidine to give 3-amino-PnH 2 in high yields (Fig. 9).…”

Section: Thermal Cyclisations Of Vinyl Fulvenesmentioning

confidence: 99%