title: Allene ether Nazarov cyclization.
abstract: The ease of synthesis and the exceptional reactivity of alkoxyallenes has led to their use in a large number of highly diverse applications. This Report describes their use in various versions of the allene ether Nazarov cyclization. Following a brief introduction to the Nazarov cyclization (Section 1), the oxidative cyclization of vinyl alkoxyallenes is discussed first (Section 2). Nazarov cyclizations of α-alkoxyallenyl vinyl ketones and of α-alkoxyallenyl vinyl tertiary carbinols are covered (Section 3). The discovery and the subsequent rational design of acetals that serve as chiral auxiliaries on the allene in highly enantioselective Nazarov cyclizations is explained (Section 4). Interrupted Nazarov cyclizations of alkoxyallenes that are generated in situ from the isomerization of propargyl ethers on solid supports are discussed, including the evolution of a highly diastereoselective, chiral auxiliary controlled version of the reaction. Some applications of the methodology to natural products total synthesis have been included so as to provide the reader with benchmarks with which to judge the utility of the methodology.
authors.affiliation: University of Hawaii, 2545 The Mall, Honolulu, Hawaii 96822, USA. tius@hawaii.edu.
authors.forename: Marcus A
authors.initials: MA
authors.lastname: Tius
mesh_terms: D000438:Alcohols / Q000138:chemical synthesis / Q000737:chemistry; D000466:Alkadienes / Q000138:chemical synthesis / Q000737:chemistry*; D000480:Alkynes / Q000138:chemical synthesis / Q000737:chemistry; D000588:Amines / Q000138:chemical synthesis / Q000737:chemistry; D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry; D060326:Chemistry Techniques, Synthetic / Q000379:methods*; D003500:Cyclization; D003517:Cyclopentanes / Q000138:chemical synthesis / Q000737:chemistry; D004987:Ethers / Q000138:chemical synthesis / Q000737:chemistry; D007097:Imines / Q000138:chemical synthesis / Q000737:chemistry; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry; D010087:Oxides / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000438:Alcohols; D000466:Alkadienes; D000480:Alkynes; D000588:Amines; D001688:Biological Products; D003517:Cyclopentanes; D004987:Ethers; D007097:Imines; D007659:Ketones; D010087:Oxides; C059688:alkoxyl radical; C531209:propargyl ether; C025947:propadiene