Hydroxymercuration-demercuration of 3-carene

Arbuzöv, B. A.; Ratner, V. V.; Isaeva, Z. G.; Kazakova, E. Kh.

doi:10.1007/bf00857796

Cited by 1 publication

(1 citation statement)

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“…Oxidation of the latter alcohol with a variety of oxidizing agents (MnO 2 , PCC, PDC, Swern, etc.) led to mixtures of the desired exomethylene ketone (−)- 31 5c, and its endocyclic regioisomer (+)- 32 in various ratios but always with 32 being the major product. Finally, a catalytic modification of Dess−Martin oxidation [TEMPO, PhI(OAc) 2 , CH 2 Cl 2 , rt, 5 h] afforded (−)- 31 as the major product (83%); under these conditions, the endo -isomer (+)- 32 was formed in less than 10% yield.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of New Chiral 2,2‘-Bipyridine Ligands and Their Application in Copper-Catalyzed Asymmetric Allylic Oxidation and Cyclopropanation

et al. 2003

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A series of modular bipyridine-type ligands 1 and 3-9 has been synthesized via a de novo construction of the pyridine nucleus. The chiral moieties of these ligands originate from the isoprenoid chiral pool, namely, beta-pinene (10 --> 1), 3-carene (14 --> 3 and 5), 2-carene (28 --> 4), alpha-pinene (43 --> 6-8), and dehydropregnenolone acetate (48 --> 9), respectively. Copper(I) complexes, derived from these ligands and (TfO)(2)Cu (1 mol %) upon an in situ reduction with phenylhydrazine, exhibit good enantioselectivity (up to 82% ee) and unusually high reaction rate (typicaly 30 min at room temperature) in allylic oxidation of cyclic olefins (52 --> 53). Copper-catalyzed cyclopropanation proceeded with < or =76% enantioselectivity and approximately 3:1 to 99:1 trans/cis-diastereoselectivity (54 --> 55 + 56). The level of the asymmetric induction is discussed in terms of the ligand architecture that controls the stereochemical environment of the coordinated metal.

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