Jean-Marc Pons

Climate-driven diversification in two widespread Galerida larks

BackgroundThe major impact of Plio-Pleistocene climatic oscillations on the current genetic structure of many species is widely recognised but their importance in driving speciation remains a matter of controversies. In addition, since most studies focused on Europe and North America, the influence of many other biogeographic barriers such as the Sahara remains poorly understood. In this paper, climate-driven diversification was investigated by using a comparative phylogeographic approach in combination with phenotypic data in two avian species groups distributed on both sides of the deserts belt of Africa and Asia. In particular, we tested whether: 1) vicariance diversification events are concomitant with past climatic events; and 2) current ecological factors (using climate and competition as proxies) contribute to phenotypic divergence between allopatric populations.ResultsMitochondrial and nuclear sequence data indicated that the crested and Thekla lark species groups diverged in the early Pliocene and that subsequent speciation events were congruent with major late Pliocene and Pleistocene climatic events. In particular, steep increase in aridity in Africa near 2.8 and 1.7 million years ago were coincident with two north-south vicariance speciation events mediated by the Sahara. Subsequent glacial cycles of the last million years seem to have shaped patterns of genetic variation within the two widespread species (G. cristata and G. theklae). The Sahara appears to have allowed dispersal from the tropical areas during climatic optima but to have isolated populations north and south of it during more arid phases. Phenotypic variation did not correlate with the history of populations, but was strongly influenced by current ecological conditions. In particular, our results suggested that (i) desert-adapted plumage evolved at least three times and (ii) variation in body size was mainly driven by interspecific competition, but the response to competition was stronger in more arid areas.ConclusionClimatic fluctuations of the Plio-Pleistocene strongly impacted diversification patterns in the Galerida larks. Firstly, we found that cladogenesis coincides with major climatic changes, and the Sahara appears to have played a key role in driving speciation events. Secondly, we found that morphology and plumage were strongly determined by ecological factors (interspecific competition, climate) following vicariance.

A synthesis of (−)-tetrahydrolipstatin

Abstract A Lewis acid-catalysed [2+2]-cycloaddition of n-hexyl trimethylsilyl ketene (4) to (3R)-3-(benzyloxy)-tetradecanal (3) is the key step in a synthesis of the β-lactone moiety of the antiobesity agent (−)-tetrahydrolipstatin (2).

Stereocontrol of All‐Carbon Quaternary Centers through Enantioselective Desymmetrization of Meso Primary Diols by Organocatalyzed Acyl Transfer

The symmetry breaking of meso primary diols bearing a tetrahydropyran ring was employed, using catalytic asymmetric acyl transfer, to control all-carbon quaternary stereocenters. The planar chiral Fu DMAP catalyst was used in this reaction to reach a high degree of enantioselectivity (up to 97:3 e.r.) through a synergic effect combining a desymmetrization step and a kinetic resolution. Moreover, a beneficial effect was exhibited by C6F6 solvent, yielding the first example of an organocatalyzed asymmetric acyl transfer. The desymmetrized monoesters were then used to obtain, after a straightforward ring opening sequence, complex polyketide building blocks bearing all-carbon quaternary stereocenters.

Reductive coupling of α,β-enones I: Reduction of methyl-vinyl ketone and mesityl oxide.

Abstract Reductive coupling of methyl-vinyl ketone with TiCl 4 -Mg gives pinacol 1 (25%). According to the reducing agents, mesityl oxide yields 2,4,5,7-tetramethyl-octa-2,4,6-triene 3 (with 4TiCl 3 -LialH 4 ), triene 3 or 2,4,5,7-tetramethyl-octa-2,6-dien-4,5-diol 5 (with TiCl 4 -Mg), pinacol 5 (with VCl 3 -Mg), and 2-acetyl-1,3,3,4,4-pentamethyl-cyclopentane 7 (with CrCl 3 -Mg or FeCl 3 -Mg or ZrCl 4 or ZrCl 4 -Mg) as major products.

Molecular support for a rapid cladogenesis of the woodpecker clade Malarpicini, with further insights into the genus Picus (Piciformes: Picinae)

Previous studies have suggested that the woodpecker genus Picus (Aves: Picidae) may not be monophyletic. In order to evaluate this hypothesis, we analyzed DNA sequences from all but two species of Picus, as well as from representatives of all genera in the tribe Malarpicini, within which Picus is nested. We sequenced seven loci (four autosomal, one Z-linked and two mitochondrial) with different evolutionary dynamics. The species currently placed in Picus fall into two subclades that may not form a monophyletic assemblage. Consequently, we propose to place miniaceus Pennant 1769, flavinucha Gould 1834 and mentalis Temminck 1825 in the genus Chrysophlegma Gould, 1850, while the remaining species are retained in Picus. The inclusion in our study of representatives of all genera included in the tribe Malarpicini, a group of woodpeckers which has proven difficult to resolve in several previous molecular studies, also allowed us to determine the earliest divergences within this clade. The results suggest that the low level of basal resolution in Malarpicini is attributable to multiple cladogenetic events in a short period of time rather than insufficient character sampling. This conclusion is supported by the observation of nucleotide insertion-deletions that support mutually exclusive phylogenetic hypotheses in different gene trees. We attribute this pattern of incongruent indels, together with short internodes in the tree, to incomplete lineage sorting.

A convergent approach to (-)-callystatin A based on local symmetry.

The key is symmetry! A convergent synthetic approach of the highly cytotoxic natural product (-)-callystatin A was developed assembling three fragments through Julia-Kocienski olefination and Stille cross-coupling. The new strategy relies on a pivotal local symmetry of the target molecule. In this preliminary study, particular attention was devoted to facilitate the catalytic enantiocontrol of strategic stereogenic centers present in each of the fragments (see scheme).

Assortative Mating without Complete Reproductive Isolation in a Zone of Recent Secondary Contact between Herring Gulls (Larus argentatus) and Caspian Gulls (L. cachinnans)

ABSTRACT. The zone of secondary contact between Herring Gulls (Larus argentatus) and Caspian Gulls (L. cachinnans) in central Poland is characterized by high levels of introgreeRzemyscular mars several phenotypic characters, with the exception of bare-parts coloration. These patterns suggest a role for coloration as a premating isolating barrier between these species. We investigated the degree of reproductive isolation in this zone of secondary contact by testing three hypotheses: (1) postmating isolation is weak or absent, (2) a partial premating isolation is present, and (3) orbital-ring color or another closely correlated trait is involved in premating isolation, which explains the signal of disruptive selection previously observed (a lower degree of introgression). We also investigated whether differences in breeding phenology could contribute to premating isolation. We found no evidence of postmating isolation, but premating isolation occurred: heterospecific pairs were significantly scarcer than expected under random mating. This assortative mating is best explained by a combination of divergent breeding phenology and mate choice influenced by orbital-ring color. However, because the differentiation in orbital-ring color between L. argentatus and L. cachinnans is incomplete and their breeding periods overlap, premating isolation is only partial. That a previous study found a high level of genetic introgression between these species suggests that reinforcement can occur only in association with sufficiently strong postmating isolation.

The Cohalogenation of 1‐N‐Vinylpyrimidinediones: A New Approach to Nucleoside Analogs

A new approach to the synthesis of nucleoside analogs has been developed, which involves initial chemo- and regioselective cohalogenation of 1-N-vinylpyrimidinediones 10a,b using N-bromosuccinimide in the presence of variously substituted propargylic alcohols. Radical carbocyclization of the resulting β-bromo propargylic ethers 17-22 then leads to 3-methylenetetrahydrofurans 23-26. In such cyclizations, different reactivities have been observed for diastereomers 22a,b obtained by cohalogenation with (R)-1-benzyloxybut-3-yn-2-ol; although the expected anti 3-methylenetetrahydrofurans 27a,b were obtained, the syn diastereomers 28a,b were only the minor constituents of a mixture in which bicyclonucleosides 29a,b were the major components. The formation of 29a,b results from a 1,6-hydrogen transfer followed by cyclization, which might be favored by a CH-π interaction in radical intermediate synII.

Reductive coupling of α,β unsaturated ketones III (+)-pulegone: An example of umpolung☆

Abstract Treatment of (+)-pulegone with TiCl 4 Mg/THF complex unexpectedly yields a) menthone (when the reaction is carried out with t-butyl alcohol),b)allylmenthadienes (when it is carried out with allylic halides), c) ketol dimers (when no additive electrophilic species is used); a bielectronic transfer mechanism, leading to an umpolung on (+)-pulegone is proposed as an explanation for the formation and the structure of the products.

Highly Enantioselective Acylation of Acyclic Meso 1,3-Diols through Synergistic Isothiourea-Catalyzed Desymmetrization/Chiroablative Kinetic Resolution.

A general and highly efficient organocatalyzed desymmetrization of acyclic meso 1,3-diols through acyl transfer using chiral isothioureas is described. The introduction of π-systems in the acyclic substrates provided new opportunities in terms of reactivity, enantioselectivity and synthetic potential. To reach this high level of enantioselectivity (up to er >99:1), the reaction proceeds through a synergistic mechanism involving a desymmetrization reaction and a chiroablative kinetic resolution process. This methodology was used with success as the sole enantioselective catalytic step (developed on a gram scale) to achieve the total synthesis of the antiosteoporotic diarylheptanoid (-)-diospongin A (7 steps).