Regioselective Coupling of Different Conjugate Esters by Magnesium Metal Reduction: A Route to Unsymmetrical Adipic Acid Esters.

A novel tactic to synthesize unsymmetrical 3-aryladipic acid esters has been developed via magnesium-promoted reductive coupling of ethyl cinnamates with methyl acrylate. In the present methodology, 3-aryladipic acid derivatives were prepared with good functional group tolerance and a wide substrate scope under very mild reaction conditions in good yields. The application of this reaction to dienic acid esters led to the successful control of the reaction to give 5-aryl-oct-3-enedioic acid esters with high regioselectivity.

Evolution of vegetation and climate variability on the Tibetan Plateau over the past 1.74 million years.

The Tibetan Plateau exerts a major influence on Asian climate, but its long-term environmental history remains largely unknown. We present a detailed record of vegetation and climate changes over the past 1.74 million years in a lake sediment core from the Zoige Basin, eastern Tibetan Plateau. Results show three intervals with different orbital- and millennial-scale features superimposed on a stepwise long-term cooling trend. The interval of 1.74-1.54 million years ago is characterized by an insolation-dominated mode with strong ~20,000-year cyclicity and quasi-absent millennial-scale signal. The interval of 1.54-0.62 million years ago represents a transitional insolation-ice mode marked by ~20,000- and ~40,000-year cycles, with superimposed millennial-scale oscillations. The past 620,000 years are characterized by an ice-driven mode with 100,000-year cyclicity and less frequent millennial-scale variability. A pronounced transition occurred 620,000 years ago, as glacial cycles intensified. These new findings reveal how the interaction of low-latitude insolation and high-latitude ice-volume forcing shaped the evolution of the Tibetan Plateau climate.

East Asian summer monsoon precipitation variability since the last deglaciation.

The lack of a precisely-dated, unequivocal climate proxy from northern China, where precipitation variability is traditionally considered as an East Asian summer monsoon (EASM) indicator, impedes our understanding of the behaviour and dynamics of the EASM. Here we present a well-dated, pollen-based, ~20-yr-resolution quantitative precipitation reconstruction (derived using a transfer function) from an alpine lake in North China, which provides for the first time a direct record of EASM evolution since 14.7 ka (ka = thousands of years before present, where the "present" is defined as the year AD 1950). Our record reveals a gradually intensifying monsoon from 14.7-7.0 ka, a maximum monsoon (30% higher precipitation than present) from ~7.8-5.3 ka, and a rapid decline since ~3.3 ka. These insolation-driven EASM trends were punctuated by two millennial-scale weakening events which occurred synchronously to the cold Younger Dryas and at ~9.5-8.5 ka, and by two centennial-scale intervals of enhanced (weakened) monsoon during the Medieval Warm Period (Little Ice Age). Our precipitation reconstruction, consistent with temperature changes but quite different from the prevailing view of EASM evolution, points to strong internal feedback processes driving the EASM, and may aid our understanding of future monsoon behaviour under ongoing anthropogenic climate change.