275804-95-0Relevant academic research and scientific papers
Enantioselective intramolecular aldehyde α-alkylation with simple olefins: Direct access to homo-ene products
Comito, Robert J.,Finelli, Fernanda G.,Macmillan, David W. C.
, p. 9358 - 9361 (2013/07/26)
A highly selective method for the synthesis of asymmetrically substituted carbocycles and heterocycles from unactivated aldehyde-olefin precursors has been achieved via enantioselective SOMO-catalysis. Addition of a catalytically generated enamine radical cation across a pendent olefin serves to establish a general asymmetric strategy toward the production of a wide range of formyl-substituted rings with alkene transposition. Conceptually, this novel mechanism allows direct access to "homo-ene"-type products.
Synthesis of (-)-okilactomycin by a prins-type fragment-assembly strategy
Tenenbaum, Jason M.,Morris, William J.,Custar, Daniel W.,Scheidt, Karl A.
, p. 5892 - 5895 (2011/08/04)
All things converge: A highly convergent synthesis of (-)-okilactomycin utilizes a Prins-type Maitland-Japp cyclization for the fragment assembly of two complex intermediates (see scheme). The synthesis also employs a highly diastereoselective Lewis acid promoted Diels-Alder reaction and an olefin ring-closing metathesis to close a strained 11-membered macrocycle.
Efficient and stereoselective synthesis of yellow scale pheromone via alkyne haloboration, Zr-catalyzed asymmetric carboalumination of alkenes (ZACA reaction), and Pd-catalyzed tandem negishi coupling
Xu, Zhaoqing,Negishi, Ei-Ichi
supporting information; experimental part, p. 4311 - 4314 (2009/06/06)
(Chemical Equation Presented) A Pd-catalyzed reaction of allylzincs with the 1-octyne bromoboration product gives the desired allyl-alkenyl coupling products in good yields except with H2C=CHCH2ZnBr. This reaction is suitable for con
Synthesis of the C1-C16 fragment of ionomycin using a neutral (η3-allyl)iron complex
Cooksey, John P.,Kocienski, Philip J.,Li, Ying-Fa,Schunk, Stefan,Snaddon, Thomas N.
, p. 3325 - 3336 (2008/09/16)
Key steps in the synthesis of the C1-C16 polyketide fragment of ionomycin were the nucleophilic addition of an organocuprate to a neutral (η3-allyl)iron complex and the construction of a β-diketone moiety by the Rh-catalysed rearrangement of an
Optical rotation computation, total synthesis, and stereochemistry assignment of the marine natural product Pitiamide A
Ribe, Seth,Kondru, Rama K.,Beratan, David N.,Wipf, Peter
, p. 4608 - 4617 (2007/10/03)
We report the joint application of ab initio computations and total synthesis to assign the absolute configuration of a new natural product. The expected specific rotations of the (7S,10R)- and (7R,10R)-isomers of pitiamide A in a CHCl3 solvent continuum model were determined as +8 and -39, respectively, by CADPAC calculations of the electric-dipole-magnetic-dipole polarizability tensor. Total syntheses of these two stereoisomers of the marine metabolite were achieved by a convergent strategy that utilized Evans' oxazolidinone alkylation, a novel water-accelerated modification of Negishi's zirconocene-catalyzed asymmetric carbometalation as well as an unusual segment condensation via Mitsunobu alkylation of a nosyl-activated amide. The experimental optical rotation measurements confirmed the results of the computational optical rotation predictions. On the basis of NMR comparisons, the configuration of pitiamide A was assigned as (7R,10R). These studies highlight the considerable structural significance of [α]D data, but, because the optical rotation of the natural product was different from either synthetic diastereomer, our work serves also as an illustration of potential problems with obtaining accurate experimental [α]D data for natural samples.
