2018
DOI: 10.1021/acs.orglett.8b00153
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Rhodium-Catalyzed Asymmetric Conjugate Alkynylation/Aldol Cyclization Cascade for the Formation of α-Propargyl-β-hydroxyketones

Abstract: A rhodium-catalyzed conjugate alkynylation/aldol cyclization cascade was developed. Densely functionalized cyclic α-propargyl-β-hydroxyketones were synthesized with simultaneous formation of a C(sp)-C(sp) bond, a C(sp)-C(sp) bond, as well as three new contiguous stereocenters. The transformation was achieved with excellent enantio- and diastereoselectivities using BINAP as the ligand. The synthetic utility of the newly installed alkynyl moiety was exhibited by subjecting the products to an array of derivatizat… Show more

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Cited by 24 publications
(9 citation statements)
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“…These ring closures lead to densely functionalized cyclopentanes and -hexanes with three or four contiguous stereocenters. Various diastereotopic group-selective aldol reactions have already been described, including copper-catalyzed addition of hydride , and boron and carbon nucleophiles , (Scheme , bottom) . We now disclose here a cyclization of this system initiated by conjugate silylation where the choice of the zinc- or boron-based silicon (pro)­nucleophile determines the relative configuration of the bicyclic product (Scheme , bottom) …”
mentioning
confidence: 91%
“…These ring closures lead to densely functionalized cyclopentanes and -hexanes with three or four contiguous stereocenters. Various diastereotopic group-selective aldol reactions have already been described, including copper-catalyzed addition of hydride , and boron and carbon nucleophiles , (Scheme , bottom) . We now disclose here a cyclization of this system initiated by conjugate silylation where the choice of the zinc- or boron-based silicon (pro)­nucleophile determines the relative configuration of the bicyclic product (Scheme , bottom) …”
mentioning
confidence: 91%
“…In 2018, Lautens and co-workers reported rhodium-catalyzed alkynylation/aldol cyclization sequence of ketoenones, which can synthesize cyclic α-propargyl-β-hydroxyketones with high enantio- and diastereoselectivity (Scheme 28). 46 Using ( S )-BINAP as the chiral ligand, a wide range of six-membered products were synthesized with excellent enantio- and diastereoselectivities of 89–99% ee and dr >20 : 1. In the proposed reaction mechanism, alkynylrhodation of enone by rhodium-alkynyl species B generates (oxa-π-allyl)rhodium intermediate C .…”
Section: Alkynyl Carbon–carbon Bond Cleavage Of Propargylic Alcoholsmentioning
confidence: 99%
“…Lautens recently disclosed an alkynylation/aldol cyclization sequence of keto-enones 61, affording cyclic α-propargyl-βhydroxyketones 63 with high enantio-and diastereoselectivity (Scheme 11). 59 A broad range of six-membered adducts was furnished, bearing aliphatic and aromatic groups on both sides of the keto-enone. Several bulky alkynes, including aliphatic ones, were tolerated, but terminal alkynes lead to homodimerization instead.…”
Section: β-Alkynyl Elimination With Rhodiummentioning
confidence: 99%