Main conclusion
Lignan impregnation of the reaction zone wood protects against oxidative degradation by fungi. Traumatic resin canals may play roles in the underlying signal transduction, synthesis, and translocation of defense compounds.
Abstract
Tree defense against xylem pathogens involves both constitutive and induced phenylpropanoids and terpenoids. The induced defenses include compartmentalization of compromised wood with a reaction zone (RZ) characterized by polyphenol deposition, whereas the role of terpenoids has remained poorly understood. To further elucidate the tree–pathogen interaction, we profiled spatial patterns in lignan (low-molecular-weight polyphenols) and terpenoid content in Norway spruce (Picea abies) trees showing heartwood colonization by the pathogenic white-rot fungus Heterobasidion parviporum. There was pronounced variation in the amount and composition of lignans between different xylem tissue zones of diseased and healthy trees. Intact RZ at basal stem regions, where colonization is the oldest, showed the highest level and diversity of these compounds. The antioxidant properties of lignans obviously hinder oxidative degradation of wood: RZ with lignans removed by extraction showed significantly higher mass loss than unextracted RZ when subjected to Fenton degradation. The reduced diversity and amount of lignans in pathogen-compromised RZ and decaying heartwood in comparison to intact RZ and healthy heartwood suggest that α-conindendrin isomer is an intermediate metabolite in lignan decomposition by H. parviporum. Diterpenes and diterpene alcohols constituted above 90% of the terpenes detected in sapwood of healthy and diseased trees. A significant finding was that traumatic resin canals, predominated by monoterpenes, were commonly associated with RZ. The findings clarify the roles and fate of lignan during wood decay and raise questions about the potential roles of terpenoids in signal transduction, synthesis, and translocation of defense compounds upon wood compartmentalization against decay fungi.
Dibromocyclopropanations are conventionally done by addition of dibromocarbene to alkenes under phase-transfer conditions in batch reactions using a strong base (50% NaOH (aq)), vigorous stirring and long reaction times. We have shown that cyclopropanation of unsaturated alcohols can be done under ambient conditions using continuous flow chemistry with 40% (w/w) NaOH (aq) as the base. The reactions were generally rapid; the yields were comparable to yields reported in the literature for the conventional batch reaction
Conventional batch dibromocyclopropanations by reaction of bromoform and alkenes under phase-transfer conditions require strong base (50% NaOH (aq)), vigorous stirring, and often long reaction times. Using flow chemistry in a microreactor, the reactions were found to be smooth, rapid, and high-yielding under ambient conditions when 40% (w/w) NaOH was used as the base. The reaction has been tested with a representative selection of alkenes, displaying a variety of structural features.
When subjected to HBr/HOAc in polar solvents like acetic acid, 6-(1-methylethylidene)-bicyclo[3.2.0]heptanes undergo a ring expansion reaction yielding 2-bromo-3,3-dimethylbicyclo[3.3.0]octane and 3-bromo-2,2-dimethylbicyclo[3.3.0]octane. Several other isopropylidenecyclobutanes have been found to undergo the same reaction with high stereoselectivity and moderate regioselectivity. In less polar solvents like diethyl ether the ring expansion reaction is suppressed, and bromides resulting from addition of HBr to the isopropylidene double bond are obtained.
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