Li F.,Laboratory of Chemical Genomics |
Tu Q.,Laboratory of Chemical Genomics |
Chen S.,Laboratory of Chemical Genomics |
Zhu L.,Chongqing University |
And 3 more authors.
Angewandte Chemie - International Edition | Year: 2017
The first enantiospecific synthesis of hispidaninA (4), a dimeric diterpenoid from the rhizomes of Isodon hispida, was achieved with a longest linear sequence of 12steps in 6.5% overall yield. A key component is the use of the abundant and naturally occurring diterpenoids (+)-sclareolide and (+)-sclareol as starting materials, which enables the gram-scale preparation of the key intermediates totarane (1) and s-trans-12E,14-labdadien-20,8β-olide (2). Subsequently a thermal or an erbium-catalyzed intermolecular Diels-Alder reaction of totarane (1) with labdadienolide (2) provide convergent and rapid access to the natural product hispidaninA (4). The synthetic studies have offered significant impetus for the efficient construction of these architecturally complex natural products. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Wu N.,Laboratory of Chemical Genomics |
Wu N.,CAS Beijing National Laboratory for Molecular |
Deng L.,Laboratory of Chemical Genomics |
Deng L.,CAS Beijing National Laboratory for Molecular |
And 8 more authors.
Chemistry - An Asian Journal | Year: 2013
Which way? Palladium thiourea catalyzed Pauson-Khand reaction of norbornene with substituted alkynoates to afford selectively either α-carboxylated adducts or β-carboxylated adducts with the reverse regioselectivity has been demonstrated for the first time. Control of the regioselectivity in this transformation is governed by the addition of LiCl. A mechanistic interpretation to account for this observed regioselectivity is presented. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.