6‐Vinylfulven

Abstract

4, 13. SCIIALTEGGER, Helv. 45, 1368 (1962). b) I). 13. R. BARTON & N. F. WOOLSEY, private Mitteilung: Im Kernresorianz-Spektrum des Alkohols I liefern die Drciringprotonen ein A BX-Spektrum mit cinem mittleren il-Wert von ca. 1,62 ppm fur dic Methylenprotonen HA und HB und einem il-Wert von 2,25 pprn fur das Methinproton Hx. Im Spcktrum des 3,5-Dinitrobcnzoates liegen die entsprechenden Signale hei ca. 1.85 resp. 2.57 ppni. Nach einer grobcn Nahcrungsrechnung erster Ordnung fur &as A BX-Spektrum des Alkohols erhalt man fur HA und 8Hrj eine Diffcrenz von 0,07 ppm und dic folgenden Kopplungskonstanten: J H H ca. 11 Hz, J H~, H~ und JH H 7-8 Hz. Die Protonen der zur Alkohol-bzw. 3, S-l>initrobenzoat-(;ruppe a-standigen Methylengruppe bildcn mit dem ilkthinproton HX ebenfalls ein A B X -Spektrum, wobei der mittlere (7-Wert von HA und HB im Alkoholca. 3,60ppm, im 3,5-Dinitrobenzoat ca. 4,GO ppm, HA -8Hu ca. 0,37 ppm, die Kopplungskonstanten ,JH H ca. 12 Hz, ca. 7,5 H z und J H~, H ,~ ca. 6,5 Hz betragen. Die Fulvenprotonen geben Anlass zu eincm A,B,-Spektrum mit SHA = 6.45 ppm, B H B = 6,07 pprn fur dcn Alkohol und8HA = 6,50ppm, ~H B = 6.11 pprn fur das 3,5-Dinitrobcnzoat. Das Signaldes Rlkoholprotons befindet sich in Tetrachlorkohlenstoff bci 3,02 pprn unil lasst sich durch Schiitteln der L8sung mit schwercm Wasser wcitgehend entfernen. A , B B, x A , R

An expedient synthesis of 6-Vinylfulvene

“…The product, 6-vinylfulvene ( 1 ), was isolated after aqueous work-up as a red oil after flash chromatography in 67% yield. The NMR spectrum of 1 at 500 MHz is remarkably simpler than the counterpart previously reported by Neuenschwander et al 7 in that at 500 MHz the spin systems are now first-order and peak assignments rendered exceptionally facile.…”

Synthesis of organometallic pentalenide complexes

“…However, 6-vinyl fulvene is again not trivial to synthesise. Neuenschwander reported two preparations: the first reacting 1-hydroxymethyl-spiro- [2,4]hepta-4,6-diene with HCl, 24 the second reacting NaCp with 3-acetoxy-3-chloro-1-propene. 25 Both routes give low yields (10% and 20%, respectively) due to significant side reactions occurring.…”

A general intramolecular Diels–Alder approach to tricyclic sesquiterpenes: stereoselective total syntheses of (±)-sinularene and (±)-5-epi-sinularene

“…These considerations indicated that the substituted triene 13 (Scheme 2) was a desirable intermediate target, as it possessed these features as well as containing all 15 carbon atoms required for the natural product. 4 The substituted triene 13 was elaborated from a series of condensations commencing with the aldehyde 7, which was prepared by oxidation of the corresponding primary alcohol (20,21) with active manganese dioxide (19). The initial aldol condensation of 7 with the anion derived from methyl 3-methylbutyrate and lithium diisopropylamide (LDA) was conducted at -78°C in tetrahydrofuran (THF).…”