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Synthesis of Methylene‐ and Alkylidenecyclopropane Derivatives
Author(s) -
Audran Gérard,
Pellissier Hélène
Publication year - 2010
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200900872
Subject(s) - chemistry , cyclopropane , medicinal chemistry , methylene , trimethylsilyl , enamine , nucleophile , electrophile , moiety , organic chemistry , dimethoxyethane , stereochemistry , ring (chemistry) , electrode , electrolyte , catalysis
Since the methylenecyclopropane moiety is found in many biologically active natural substances, the synthesis of methylene‐ and alkylidenecyclopropanes remains a considerable challenge. In addition, an attractive feature is their surprising stability, accompanied by a high level of strain, conferring on them an otherwise unattainable chemical reactivity. The growing interest in the chemistry of these compounds has in its turn stimulated the development of alternative approaches to their skeleton, aimed at selectively introducing structural and chemical diversification. The three principal methods to synthesize these important compounds are based on the formation of the cyclopropane ring, the use of preformed cyclopropanes, and the use of preformed methylene‐ and alkylidenecyclopropanes. Abbreviations: Ac: acetyl; Ar: aryl; Bn: benzyl; Boc: tert ‐butoxycarbonyl; Box: bisoxazoline; BTMSA: bis(trimethylsilyl)amide; Bu: butyl; Bz: benzoyl; C: cyclo; Cod: cyclooctadiene; Cp: cyclopentadienyl; Cy: cyclohexyl; Dba: ( E,E )‐dibenzylideneacetone; DBU: 1,8‐diazabicyclo[5.4.0]undec‐7‐ene; DCE: 1,2‐dichloroethane; de : diastereomeric excess; DEAD: diethyl azodicarboxylate; DMAc: N,N ‐dimethylacetamide; DME: 1,2‐dimethoxyethane; DMF: dimethylformamide; DOSP: N ‐ p ‐dodecylbenzenesulfonylprolinate; Dppb: 1,4‐bis(diphenyl)phosphinoborane; Dppe: bis(diphenylphosphino) ethene; E: electrophile; ee : enantiomeric excess; Et: ethyl; Hex: hexyl; L: ligand; LDA: lithium diisopropylamide; LG: leaving group; MCPBA: 3‐chloroperoxybenzoic acid; Me: methyl; MEM: methoxyethoxymethyl; MOM: methoxymethyl; Mp: morpholinyl; Ms: mesyl; Naph: naphthyl; NFSI: N ‐fluorobenzenesulfonimide; Ns: nosyl; Nu: nucleophile; Pent: pentyl; Ph: phenyl; PMB: p ‐methoxybenzoyl; Pr: propyl; Py: pyridyl; SEM: 2‐(trimethylsilyl)ethoxymethyl; TASF: tris(dimethylamino)sulfonium difluorotrimethyl silicate; TBAF: tetra‐ n ‐butylammonium fluoride; TBS: tert ‐butyldimethylsilyl; TEA: triethylamine; Tedicyp: cis,cis,cis ‐1,2,3,4‐tetrakis(diphenylphosphinomethyl)cyclopentane; Tf: trifluoromethanesulfonyl; TFP: tris(2‐furyl)phosphine; THF: tetrahydrofuran; THP: tetrahydropyran; TMS: trimethylsilyl; Tol: tolyl; Ts: 4‐toluenesulfonyl (tosyl).