Impacts of marine instability across the East Antarctic Ice Sheet on Southern Ocean dynamics

Recent observations and modelling studies have demonstrated the potential for rapid and substantial retreat of large sectors of the East Antarctic Ice Sheet (EAIS). This has major implications for ocean circulation and global sea level. Here we examine the effects of increasing meltwater from the Wilkes Basin, one of the major marine-based sectors of the EAIS, on Southern Ocean dynamics. Climate model simulations reveal that the meltwater flux rapidly stratifies surface waters, leading to a dramatic decrease in the rate of Antarctic Bottom Water (AABW) formation. The surface ocean cools but, critically, the Southern Ocean warms by more than 1 degrees C at depth. This warming is accompanied by a Southern Ocean-wide “domino effect”, whereby the warming signal propagates westward with depth. Our results suggest that melting of one sector of the EAIS could result in accelerated warming across other sectors, including the Weddell Sea sector of the West Antarctic Ice Sheet. Thus, localised melting of the EAIS could potentially destabilise the wider Antarctic Ice Sheet

10Be in last deglacial climate simulated by ECHAM5-HAM – Part I: Climatological influences on 10Be deposition

Reconstruction of solar irradiance has only been possible for the Holocene so far. During the last deglaciation, two solar proxies (10Be and 14C) deviate strongly, both of them being influenced by climatic changes in a different way. This work addresses the climate influence on 10Be deposition by means of ECHAM5-HAM atmospheric aerosol–climate model simulations, forced by sea surface temperatures and sea ice extent created by the CSIRO Mk3L coupled climate system model. Three time slice simulations were performed during the last deglaciation: 10 000 BP ("10k"), 11 000 BP ("11k") and 12 000 BP ("12k"), each 30 yr long. The same, theoretical, 10Be production rate was used in each simulation to isolate the impact of climate on 10Be deposition. The changes are found to follow roughly the reduction in the greenhouse gas concentrations within the simulations. The 10k and 11k simulations produce a surface cooling which is symmetrically amplified in the 12k simulation. The precipitation rate is only slightly reduced at high latitudes, but there is a northward shift in the polar jet in the Northern Hemisphere, and the stratospheric westerly winds are significantly weakened. These changes occur where the sea ice change is largest in the deglaciation simulations. This leads to a longer residence time of 10Be in the stratosphere by 30 (10k and 11k) to 80 (12k) days, increasing the atmospheric concentrations (25–30% in 10k and 11k and 100% in 12k). Furthermore the shift of westerlies in the troposphere leads to an increase of tropospheric 10Be concentrations, especially at high latitudes. The contribution of dry deposition generally increases, but decreases where sea ice changes are largest. In total, the 10Be deposition rate changes by no more than 20% at mid- to high latitudes, but by up to 50% in the tropics. We conclude that on "long" time scales (a year to a few years), climatic influences on 10Be deposition remain small (less than 50%) even though atmospheric concentrations can vary significantly. Averaged over a longer period, all 10Be produced has to be deposited by mass conservation. This dominates over any climatic influences on 10Be deposition. Snow concentrations, however, do not follow mass conservation and can potentially be impacted more by climate due to precipitation changes. Quantifying the impact of deglacial climate modulation on 10Be in terms of preserving the solar signal locally is analysed in an accompanying paper (Heikkilä et al., 10Be in late deglacial climate simulated by ECHAM5-HAM – Part 2: Isolating the solar signal from 10Be deposition). © Author(s) 2013

Catalytic enantioselective Minisci-type addition to heteroarenes.

Basic heteroarenes are a ubiquitous feature of pharmaceuticals and bioactive molecules, and Minisci-type additions of radical nucleophiles are a leading method for their elaboration. Despite many Minisci-type protocols that result in the formation of stereocenters, exerting control over the absolute stereochemistry at these centers remains an unmet challenge. We report a process for addition of prochiral radicals, generated from amino acid derivatives, to pyridines and quinolines. Our method offers excellent control of both enantioselectivity and regioselectivity. An enantiopure chiral Brønsted acid catalyst serves both to activate the substrate and induce asymmetry, while an iridium photocatalyst mediates the required electron transfer processes. We anticipate that this method will expedite access to enantioenriched small-molecule building blocks bearing versatile basic heterocycles

Hydrogen Atom Transfer-Driven Enantioselective Minisci Reaction of Amides.

Minisci-type reactions constitute one of the most powerful methods for building up complexity around basic heteroarenes. The most desirable variants involve formal oxidative coupling of a C-H bond on each partner, leading back to the simplest possible starting materials. We herein disclose a method that enables such a coupling of linear amides and heteroarenes with full control of enantioselectivity at the newly formed stereocenter as well as site selectivity on both the heteroarene and the amide. This is achieved by the use of a chiral phosphoric acid catalyst in conjunction with diacetyl as a combined hydrogen atom transfer reagent and oxidant. Diacetyl is directly photoexcitable, and thus, no extraneous photocatalyst is required: an added feature that contributes to the simplicity and practicality of the protocol.EPSRC, GlaxoSmithKline, ER

A Computational and Experimental Investigation of the Origin of Selectivity in the Chiral Phosphoric Acid Catalyzed Enantioselective Minisci Reaction.

The Minisci reaction is one of the most valuable methods for directly functionalizing basic heteroarenes to form carbon-carbon bonds. Use of prochiral, heteroatom-substituted radicals results in stereocenters being formed adjacent to the heteroaromatic system, generating motifs which are valuable in medicinal chemistry and chiral ligand design. Recently a highly enantioselective and regioselective protocol for the Minisci reaction was developed, using chiral phosphoric acid catalysis. However, the precise mechanism by which this process operated and the origin of selectivity remained unclear, making it challenging to develop the reaction more generally. Herein we report further experimental mechanistic studies which feed into detailed DFT calculations that probe the precise nature of the stereochemistry-determining step. Computational and experimental evidence together support Curtin-Hammett control in this reaction, with initial radical addition being quick and reversible, and enantioselectivity being achieved in the subsequent slower, irreversible deprotonation. A detailed survey via DFT calculations assessed a number of different possibilities for selectivity-determining deprotonation of the radical cation intermediate. Computations point to a clear preference for an initially unexpected mode of internal deprotonation enacted by the amide group, which is a crucial structural feature of the radical precursor, with the assistance of the associated chiral phosphate. This unconventional stereodetermining step underpins the high enantioselectivities and regioselectivities observed. The mechanistic model was further validated by applying it to a test set of substrates possessing varied structural features.EPSRC GSSK ERC Leverhulme Trust Isaac Newton Trus