✦ LIBER ✦

The Reaction of Difluorocarbene with Bicyclo[2.2.2]octadiene

✍ Scribed by Charles W. Jefford; Arlette Delay; Timothy W. Wallace; Ulrich Burger

Publisher: John Wiley and Sons
Year: 1976
Tongue: German
Weight: 466 KB
Volume: 59
Category: Article
ISSN: 0018-019X
DOI: 10.1002/hlca.19760590708

No coin nor oath required. For personal study only.

✦ Synopsis

Abstract

The addition of difluorocarbene to bicyclo[2.2.2]octa‐2,5‐diene gave the exo and endo 1:1 cyclopropane adducts. In contrast to norbornadiene, no homo‐1,4 adduct was formed. The adducts were thermally stable under the conditions of their formation and separation (<170°). However, smooth equilibration was achieved on heating at 250° for 36 h. The same mixture resulted from either isomer. At 250° ΔΔ__G__ = 1.83 kcal/mol; the endo isomer being the more stable. Heating to higher temperatures caused decomposition, rather than further reaction to the intramolecular [2+2]cyclization products. The kinetic and thermodynamic product compositions were essentially the same on extrapolating to the same temperature, viz. endo/exo = 19–22 at 25°. The mechanisms by which the cyclo‐addition and the stereomutation of the cis‐fused cyclopropane moiety occur are discussed.

📜 SIMILAR VOLUMES

Cobalt-catalyzed [4 + 2 + 2] cycloadditi

Cobalt-catalyzed [4 + 2 + 2] cycloadditions of bicyclo[2.2.2]octadienes

✍ Rattana Kiattansakul; John K. Snyder 📂 Article 📅 1999 🏛 Elsevier Science 🌐 French ⚖ 263 KB

Silver-Promoted Reactions of Bicyclo[3.2

Silver-Promoted Reactions of Bicyclo[3.2.1]octadiene Derivatives.

✍ Ravi S. Orugunty; Dennis L. Wright; Merle A. Battiste; Khalil A. Abboud 📂 Article 📅 2010 🏛 John Wiley and Sons ⚖ 34 KB

Mechanism of the rearrangement of bicycl

Mechanism of the rearrangement of bicyclo[3.2.1]octadien-2-yl cations to bicyclo[3.3.0]octadien-2-yl cations

✍ Masayuki Kuzuya; Harold Hart 📂 Article 📅 1973 🏛 Elsevier Science 🌐 French ⚖ 165 KB

Below -60' in FSOaH/SOzClF the nonamethyl bicyclo[3.2.1 loctadien-Pyl cation J, undergoes two degenerate rearrangements, circumambulation' and a 1,2-shift of the methano bridge.2 The first of these processes is much faster than the second, and is nmr-observable,' whereas the second process was detec

Pyramidalized olefins: The stereospecifi

Pyramidalized olefins: The stereospecific conjugate reduction of a bicyclo[2.2.2]octadiene

✍ Richard Vaughan Williams; Vijay R. Gadgil; Gary G. Garner; John D. Williams; Ash 📂 Article 📅 1999 🏛 Elsevier Science 🌐 French ⚖ 107 KB

Structure determination on 2-benzenesulphonyl-3-trimethylsilylbicyclo[2.2.2]octa-2,5-diene (3) demonstrates that the double bonds are pyramidalized in the exo direction. Nucleophilic attack (conjugate reduction) on 3 parallels this pyramidalization and occurs exclusively from the endo face.

ChemInform Abstract: Cobalt- Catalyzed [

ChemInform Abstract: Cobalt- Catalyzed [4 + 2 + 2] Cycloadditions of Bicyclo[2.2.2]octadienes.

✍ Rattana Kiattansakul; John K. Snyder 📂 Article 📅 2010 🏛 John Wiley and Sons ⚖ 35 KB 👁 1 views

Cobalt-Catalyzed [4 + 2 + 2] Cycloadditions of Bicyclo[2.2.2]octadienes. -Norbornadiene (I) and the benzobarrelenes (IV) undergo cobalt-catalyzed [4 + 2 + 2] cycloaddition with the dienes (II) or (VI) to give the corresponding adducts. In contrast, analogous reaction of the bicyclo[3.2.1]octadeine

Cycloadditions, 27. The Thermal Rearrang

Cycloadditions, 27. The Thermal Rearrangement of the Bicyclo[2.2.2]- to Bicyclo[3.2.1]octadiene Moiety in Tricyclic Lactams

✍ Himbert, Gerhard ;Diehl, Klaus 📂 Article 📅 1997 🏛 John Wiley and Sons 🌐 English ⚖ 634 KB

## Abstract The tricyclic lactams 4a–h, possessing a bicyclo[2.2.2]octadiene moiety, obtained by intramolecular Diels‐Alder reaction of the vinylidene malondiamides 1a–h, generally isomerize in boiling xylene to give the new lactams 7a–h, now bearing a bicyclo[3.2.1]octadiene part. The difference i