Nucleophilic Addition of Amides to Haloalkynes: Synthesis of (Z)-ß-Halovinyl Amides as Dual Precursors of Alkylidene Carbenes and Allyl Halides.

Toward a regioselective method for the synthesis of ß-halovinyl amides, we developed a transition-metal-free nucleophilic addition reaction of amides to haloalkynes. The regioselective nucleophilic addition was achieved under solvent-free conditions using phosphonates to protonate the intermediate alkylidene carbenoids, thus suppressing their decomposition. Furthermore, we demonstrate that ß-halovinyl amides can serve as dual precursors of allyl halides and alkylidene carbenes to obtain functionalized indoles and pyrrolidones.

Invasion status of hatchery-origin pink salmon in an unstocked river at the Shiretoko World Natural Heritage Site in northern Japan.

Hatchery fish and their offspring (including hatchery-wild hybrids) have lower reproductive success than wild fish. Thus, the straying of hatchery fish may negatively impact wild populations, depending on the number of wild salmon returning and hatchery strays. We investigated the straying status of hatchery-origin pink salmon (Oncorhynchus gorbuscha), which have a higher straying rate than other salmonids, in an unstocked river at the Shiretoko World Natural Heritage Site, Japan. The hatchery strays accounted for 40.0% and 19.0% of the total samples in 2021 and 2022, respectively. These results indicate that hatchery pink salmon have invaded unstocked rivers and potentially genetically affect wild populations.

Intentional release of native species undermines ecological stability.

The massive release of captive-bred native species ("intentional release") is a pervasive method to enhance wild populations of commercial and recreational species. However, such external inputs may disrupt the sensitive species interactions that allow competing species to coexist, potentially compromising long-term community stability. Here, we use theory and long-term data of stream fish communities to show that intentional release destabilizes community dynamics with limited demographic benefit to the enhanced species. Our theory predicted that intentional release intensifies interspecific competition, facilitating the competitive exclusion of unenhanced species that otherwise stably coexist. In parallel, the excessive input of captive-bred individuals suppressed the natural recruitment of the enhanced species via intensified within-species competition. Consequently, the ecological community with the intentional release is predicted to show reduced community density with unstable temporal dynamics. Consistent with this prediction, stream fish communities showed greater temporal fluctuations and fewer taxonomic richness in rivers with the intensive release of hatchery salmon-a major fishery resource worldwide. Our findings alarm that the current overreliance on intentional release may accelerate global biodiversity loss with undesired consequences for the provisioning of ecosystem services.

Diel migration pattern of pink salmon fry in small streams.

Downstream migration is a critical stage in the anadromous salmonid life cycle, but previous studies have shown different results between rivers or surveys for the diel downstream migration pattern of the fry of the pink salmon Oncorhynchus gorbuscha. We investigated the diel migration pattern of pink salmon fry in three small streams. Our results showed that pink salmon fry migrate mainly within a few hours after sunset; 89.9% of migration occurred between 18:00 and 23:00. Therefore, the results indicated that sunset time influences the diel migration pattern of pink salmon fry in small streams. This pattern could be a predator-avoidance behaviour.

Temperature-Dependent Swimming Performance Differs by Species: Implications for Condition-Specific Competition between Stream Salmonids.

Condition-specific competition is a phenomenon by which inter-specific competitive dominance changes as a result of environment, and is an important factor determining species distribution. Congeneric charrs in Hokkaido, Japan, provide one of the best examples of condition-specific competition: Dolly Varden, Salvelinus malma, often dominate in cold streams (6-8°C), whereas white-spotted charr, Salvelinus leucomaenis, dominate in warmer streams (> 10°C). While past laboratory and field experiments have demonstrated the great advantage of white-spotted charr at higher water temperatures, the advantages of Dolly Varden at lower temperature have not always been clear. Here, we examined the effect of water temperature (6°C vs. 12°C) on the swimming ability of the two sympatric charrs using a stamina tunnel. At 6°C, the swimming ability of Dolly Varden was greater than that of white-spotted charr, but no difference was observed at 12°C. These results suggest that the temperature-mediated swimming ability differs between these species, which may explain the coexistence of the closely related species within heterogeneous habitats via condition-specific competition.

Metapopulation stability in branching river networks.

Intraspecific population diversity (specifically, spatial asynchrony of population dynamics) is an essential component of metapopulation stability and persistence in nature. In 2D systems, theory predicts that metapopulation stability should increase with ecosystem size (or habitat network size): Larger ecosystems will harbor more diverse subpopulations with more stable aggregate dynamics. However, current theories developed in simplified landscapes may be inadequate to predict emergent properties of branching ecosystems, an overlooked but widespread habitat geometry. Here, we combine theory and analyses of a unique long-term dataset to show that a scale-invariant characteristic of fractal river networks, branching complexity (measured as branching probability), stabilizes watershed metapopulations. In riverine systems, each branch (i.e., tributary) exhibits distinctive ecological dynamics, and confluences serve as "merging" points of those branches. Hence, increased levels of branching complexity should confer a greater likelihood of integrating asynchronous dynamics over the landscape. We theoretically revealed that the stabilizing effect of branching complexity is a consequence of purely probabilistic processes in natural conditions, where within-branch synchrony exceeds among-branch synchrony. Contrary to current theories developed in 2D systems, metapopulation size (a variable closely related to ecosystem size) had vague effects on metapopulation stability. These theoretical predictions were supported by 18-y observations of fish populations across 31 watersheds: Our cross-watershed comparisons revealed consistent stabilizing effects of branching complexity on metapopulations of very different riverine fishes. A strong association between branching complexity and metapopulation stability is likely to be a pervasive feature of branching networks that strongly affects species persistence during rapid environmental changes.

Parasite infection induces size-dependent host dispersal: consequences for parasite persistence.

Host dispersal is now recognized as a key predictor of the landscape-level persistence and expansion of parasites. However, current theories treat post-infection dispersal propensities as a fixed trait, and the plastic nature of host's responses to parasite infection has long been underappreciated. Here, we present a mark-recapture experiment in a single host-parasite system (larval parasites of the freshwater mussel Margaritifera laevis and its salmonid fish host Oncorhynchus masou masou) and provide, to our knowledge, the first empirical evidence that parasite infection induces size-dependent host dispersal in the field. In response to parasite infection, large fish become more dispersive, whereas small fish tend to stay at the home patch. The observed plasticity in dispersal is interpretable from the viewpoint of host fitness: expected benefits (release from further infection) may exceed dispersal-associated costs for individuals with high dispersal ability (i.e. large fish) but are marginal for individuals with limited dispersal ability (i.e. small fish). Indeed, our growth analysis revealed that only small fish hosts incurred dispersal costs (reduced growth). Strikingly, our simulation study revealed that this plastic dispersal response of infected hosts substantially enhanced parasite persistence and occupancy in a spatially structured system. These results suggest that dispersal plasticity in host species is critical for understanding how parasites emerge, spatially spread, and persist in nature. Our findings provide a novel starting point for building a reliable, predictive model for parasite/disease management.

Rhodium-Catalyzed Intramolecular C-H Bond Activation with Triazoles: Preparation of Stereodefined Pyrrolidines and Other Related Cyclic Compounds.

On treatment of triazoles having an N-sulfonyl-protected benzylamine moiety with [Rh2 (C7 H15 CO2 )4 ], intramolecular C-H bond insertion takes place at the benzylic position to give cis-N-sulfonyl-2-aryl-3-[(sulfonylimino)methyl]pyrrolidines in good yields and with highly stereoselectivities. Analogously, the similar treatment of triazoles having an ether or even an alkyl moiety affords 2-alkyl- or 2-aryl-3-[(sulfonylimino)methyl]tetrahydrofurans or a 2-alkyl-3-[(sulfonylimino)methyl]cyclopentane in good yields.

Alkylation of pyridines at their 4-positions with styrenes plus yttrium reagent or benzyl Grignard reagents.

A new regioselective alkylation of pyridines at their 4-position was achieved with styrenes in the presence of yttrium trichloride, BuLi, and diisobutylaluminium hydride (DIBAL-H) in THF. Alternatively, similar products were more simply prepared from pyridines and benzyl Grignard reagents. These reactions are not only a useful preparation of 4-substituted pyridines but are also complementary to other relevant reactions usually giving 2-substituted pyridines.

Rhodium-catalyzed intramolecular hydroarylation of 1-halo-1-alkynes: regioselective synthesis of semihydrogenated aromatic heterocycles.

The regioselective intramolecular hydroarylation of (3-halo-2-propynyl)anilines, (3-halo-2-propynyl) aryl ethers, or (4-halo-3-butynyl) aryl ethers was efficiently catalyzed by Rh2(OCOCF3)4 to give semihydrogenated aromatic heterocycles, such as 4-halo-1,2-dihydroquinolines, 4-halo-3-chromenes, or 4-(halomethylene)chromans, in good to excellent yields. Some synthetic applications taking advantage of the halo-substituents of the products are also illustrated.

Relationships between gill Na⁺,K⁺-ATPase activity and endocrine and local insulin-like growth factor-I levels during smoltification of masu salmon (Oncorhynchus masou).

We established profiles of insulin-like growth factor (IGF)-I mRNA in the liver, gill and white muscle and circulating IGF-I during smoltification of hatchery-reared masu salmon, and compared with that of gill Na(+),K(+)-ATPase (NKA) activity. Gill NKA activity peaked in May and dropped in June. Liver igf1 mRNA was high in March and decreased to low levels thereafter. Gill igf1 increased from March, maintained its high levels during April and May and decreased in June. Muscle igf1 mRNA levels were relatively high during January and April when water temperature was low. Serum IGF-I continuously increased from March through June. Serum IGF-I during March and May showed a positive correlation with NKA activity, although both were also related to fish size. These parameters were standardized with fork length and re-analyzed. As a result, serum IGF-I and gill igf1 were correlated with NKA activity. On the other hand, samples from desmoltification period (June) that had high serum IGF-I levels and low NKA activity disrupted the relationship. Expression of two IGF-I receptor (igf1r) subtypes in the gill decreased in June, which could account for the disruption by preventing circulating IGF-I from acting on the gill and retaining it in the blood. The present study suggests that the increase in gill NKA activity in the course of smoltification of masu salmon was supported by both endocrine and local IGF-I, and the decrease during desmoltification in freshwater was due at least in part to the down-regulation of gill IGF-I receptors.

Facile preparation of indoles and 1,2-benzothiazine 1,1-dioxides: nucleophilic addition of sulfonamides to bromoacetylenes and subsequent palladium-catalyzed cyclization.

Bromine as a double agent: The bromine atom in 1-bromo-1-alkynes works as an electron-withdrawing group to effect the nucleophilic addition of sulfonamides. It again plays a pivotal role in the palladium-catalyzed cyclization of the resultant (Z)-2-(sulfonylamino)-1-bromoalkenes into nitrogen heterocycles (see scheme).

Four nucleophilic additions to alkenynedioic acid derivatives in tandem; efficient one-pot synthesis of bicyclo[4.2.0]octenols.

When alkenynedioic acid derivatives were treated with a Grignard reagent, tandem cyclization and the incorporation of two molecules of the Grignard reagent occurred to give stereodefined bicyclo[4.2.0]octenols via four nucleophilic additions.

Additive-free nucleophilic addition of imidazolines and imidazoles to haloacetylenes.

Nucleophilic addition of imidazolines to 1-halo-1-alkynes takes place by simple heating in DMF without any additives to give (Z)-N-(1-halo-1-alken-2-yl)imidazolines in good yield and in a highly regio- and stereoselective manner. These reaction conditions are also valid for the similar addition of imidazoles.

Iron-mediated and -catalyzed metalative cyclization of electron-withdrawing-group-substituted alkynes and alkenes with Grignard reagents.

Treatment of ethyl (E)-5,5-bis[(benzyloxy)methyl]-8-(N,N-diethylcarbamoyl)-2-octen-7-ynoate with an iron reagent generated from FeCl(2) and tBuMgCl in a ratio of 1:4 (abbreviated as FeCl(2)/4 tBuMgCl) afforded ethyl [4,4-bis[(benzyloxy)methyl]-2-[(E)-(N,N-diethylcarbamoyl)methylene]cyclopent-1-yl]acetate in good yield. Deuteriolysis of an identical reaction mixture afforded the bis-deuterated product ethyl [4,4-bis[(benzyloxy)methyl]-2-[(E)-(N,N-diethylcarbamoyl)deuteriomethylene]cyclopent-1-yl]deuterioacetate, thus confirming the existence of the corresponding dimetalated intermediate. The latter intermediate can react with halogens or aldehydes to facilitate further synthetic transformations. The amount of FeCl(2) was reduced to catalytic levels (10 mol % relative to enyne), and catalytic cyclizations of this sort proceeded with yields comparable to those of the aforementioned stoichiometric reactions. The cyclization of diethyl (E,E)-2,7-nonadienedioate with a stoichiometric amount of FeCl(2)/4 tBuMgCl, followed by the addition of sBuOH as a proton source, afforded a mixture of 2-(ethoxycarbonyl)-3-bicyclo[3.3.0]octanone and its enol form in good yield. The use of aldehyde or ketone in place of sBuOH afforded 2-(ethoxycarbonyl)-3-bicyclo[3.3.0]octanone, which has an additional hydroxyalkyl side chain. Additionally, the metalation of a carbon-carbon unsaturated bond in N,N-diethyl-5,5-bis[(benzyloxy)methyl]-7,8-epoxy-2-octynamide or (E)-3,3-dimethyl-6-(N,N-diethylcarbamoyl)-5-hexenyl p-toluenesulfonate with FeCl(2)/4 tBuMgCl or FeCl(2)/4 PhMgBr was followed by an intramolecular alkylation with an epoxide or alkyl p-toluenesulfonate to afford 5,5-bis[(benzyloxy)methyl]-3-[(E)-(N,N-diethylcarbamoyl)methylene]-1-cyclohexanol or N,N-diethyl(3,3-dimethylcyclopentyl)acetamide after hydrolysis. In both cases, the remaining metalated portion α to the amide group was confirmed by deuteriolysis and could be utilized for an alkylation with methyl iodide.

Nucleophilic addition of sulfonamides to bromoacetylenes: facile preparation of pyrroles.

Nucleophilic addition of sulfonamides to 1-bromo-1-alkynes provided (Z)-N-(1-bromo-1-alken-2-yl)-p-toluenesulfonamides in good yield and in a highly regio- and stereoselective manner. Treatment of product (Z)-N-(1-bromo-1-octen-2-yl)-N-allyl-p-toluenesulfonamide with a palladium catalyst under Heck conditions afforded 1-(p-toluenesulfonyl)-2-hexyl-4-methylpyrrole in good yield. Other pyrroles with various substituents can also be prepared in good yield by this method.

Aryl(sulfonyl)amino group: a convenient and stable yet activated modification of amino group for its intramolecular displacement.

Aryl(sulfonyl)amino groups, readily derived from sulfonyl- or arylamines by standard methods as well as the recently introduced methods of sulfonylation and arylation, proved to be good leaving groups in intramolecular substitution reactions by various nitrogen, oxygen, and carbon nucleophiles.

Iron-catalyzed regio- and stereoselective substitution of gamma,delta-epoxy-alpha,beta-unsaturated esters and amides with Grignard reagents.

When gamma,delta-epoxy-alpha,beta-unsaturated esters or amides were treated with 2 equiv of Grignard reagents in the presence of 10-24 mol % FeCl(2), regio- and stereoselective substitution of the epoxide moiety with the Grignard reagent occurred to give exclusively delta-hydroxy-gamma-alkyl or aryl-alpha,beta-unsaturated esters or amides in good yields.

Selective deprotection of methanesulfonamides to amines.

Methanesulfonamides were deprotected to their parent amines via deprotonation and oxygenation with O(2) (g), even in the presence of other traditional sulfonamides.