Solvent-free cyclization of linear dienes using olefin metathesis and the Thorpe-Ingold effect

Journal Article · Tue Dec 29 23:00:00 EST 1992 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00053a054· OSTI ID:6201655

Forbees, M D.E.; Myers, T L; Maynard, H D; Schulz, G R ^[1]; Patton, J T; Smith, Jr, D W; Wagener, K B ^[2]

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1. Univ. of North Carolina, Chapel Hill (United States)
2. Univ. of Florida, Gainesville (United States)

The olefin metathesis reaction is of great synthetic utility in polymer chemistry. The recent development of ring-opening (ROMP) and acyclic diene (ADMET) metathesis polymerization reactions has opened new avenues for the synthesis of novel polymeric materials. Recently the authors used ADMET to synthesize several photochemically active poly(keto olefins) using the catalyst Mo(CHCMe[sub 2]Ph)(NAr)(OCMe(CF[sub 3])[sub 2])[sub 2] (Ar = 2,6-diisopropylphenyl) (1) developed by Schrock and co-workers in 1990. In the course of that work, they discovered that neat samples of highly substituted dienes will cyclize quantitatively via metathesis to give difunctional five- and seven-membered rings instead of the expected linear polymer. Examples of substituted diene cyclizations by metathesis even in the presence of a solvent are rare. Their systematic exploitation in organic synthesis has therefore been limited to two recent studies by Fu and Grubbs, who cyclized several substituted diene ethers, amines, and amides to unsaturated oxygen and nitrogen heterocycles. Cyclization of unsubstituted dienes in various solvents has been reported, but complete conversion occurred in only a few cases. Formation of cyclic alkene oligomers from back-biting during the ROMP reaction is also known. The reactions reported here are unusual in that they are intermolecular between catalyst and substrate, yet can give 100% yield of product solely from the monomer in the absence of solvent. 13 refs.

• OSTI ID: 6201655
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 114:27; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COMPLEXES
CONVERSION
CYCLIZATION
DIENES
HYDROCARBONS
KETONES
MOLYBDENUM COMPLEXES
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
POLYENES
POLYMERIZATION
SYNTHESIS
TRANSITION ELEMENT COMPLEXES