The chemistry of preformed enamines, especially their use as enolate equivalents, has been a well-investigated area of research since the early 1950s. However, enamine catalysis, the catalysis of ...carbonyl transformations via enamine intermediates by using primary and secondary amines as catalysts, has only been fully appreciated as a powerful strategy for asymmetric synthesis since the beginning of this century. Contributions from this laboratory to the revitalized interest in asymmetric enamine catalysis are summarized in this Account.
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Electrolytes with a high lithium transference number linked with high ionic conductivity are urgently needed for high power battery operation. In this work, we present newly synthesized lithium ...tetra(trifluoromethanesulfonyl)propene as a salt-in-glyme-based “salt-in-solvent” electrolyte. We employ impedance spectroscopy in symmetric Li/electrolyte/Li cells and pulsed field gradient nuclear magnetic resonance spectroscopy to investigate the lithium conduction mechanism. We find predominant lithium conductivity with very high lithium transference numbers (∼70% from the polarization experiments) and three times higher ionic conductivity compared to well-known lithium triflate in diglyme electrolyte. This is a consequence of the reduced mobilities of large anions linked with improved ionic dissociation.
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During the last six years the asymmetric catalysis of carbonyl transformations via iminium ion and enamine intermediates using chiral amines as organocatalysts has grown most remarkably. In this ...personal account an overview of this area is given. The field can be divided into two sub areas: (a) Iminium catalysis, which is typically used for cycloadditions and conjugate additions to enals and enones and (b) Enamine catalysis, which is commonly used in electrophilic alpha-substitution reactions of ketones and aldehydes. A common origin of the two catalysis principles is proposed and their recent merger in tandem sequences is discussed.
Nerve injury of the saphenous nerve or infrapatellar branch seems to be a frequent complication following knee surgery or trauma. Denervation results vary, and in some cases, no pain relief is ...achieved. This might be due to anatomic variation. The purpose of this anatomical study is to identify the variation in the course of the infrapatellar branch and saphenous nerve.
We dissected 18 cadavers from adult donors. Medial to the knee, the saphenous nerve and infrapatellar branch were identified and followed proximally to the point where the infrapatellar branch branched from the saphenous nerve. The location where the infrapatellar branch came off from the saphenous nerve relative to the knee joint and where it passed the knee joint were measured.
A total of 23 infrapatellar branches were found. We identified 10 branches between 0–10 cm proximal to the knee joint, 3 branches at 10–20 cm, and 9 branches at >20 cm. Between the patella and semitendinosus tendon, the knee joint was crossed by 5 branches in the anterior, 15 in the middle, and 2 in the posterior one-third.
The origin of the infrapatellar branch and the location at which it passes the knee are highly variable. This, in addition to people having multiple branches, might explain why denervation is frequently unsuccessful. Based on the anatomical findings, we propose a more proximal diagnostic nerve block to help differentiate between a distal-middle or proximal origin of the infrapatellar branch. Appropriate placement of the nerve block might help identify people who benefit from denervation.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Residual limb pain (RLP) is associated with (partial) extremity amputations and is defined as pain felt in the remaining part of the amputated limb. A common cause of RLP is neuroma formation after ...nerve transections. Neuromas can be very painful and severely debilitating pathologies, preventing prosthetic use, reducing quality of life, and requiring medication. Residual limb pain and symptomatic neuromas are often not properly recognized by physicians explaining the varying prevalence in the literature. This systematic review and meta-analysis aim to provide a comprehensive overview of published literature on the prevalence of RLP and symptomatic neuroma after lower extremity amputation. Studies reporting the prevalence of RLP and symptomatic neuroma pain in patients who have had a lower extremity amputation published between 2000 and 2020 were identified in PubMed and Embase. Random-effects meta-analyses of proportions were performed to quantify the prevalence of RLP and symptomatic neuroma. Subgroups were identified and analysed. For RLP, the pooled prevalence was 59% (95% CI: 51-67). For symptomatic neuromas, the pooled prevalence was 15% (95% CI: 7-28). Residual limb pain subgroup analysis showed statistically significant higher prevalence in patients aged >50 years, follow-up >2 years, and in studies using a self-administered questionnaire for data collection. The prevalence of RLP and symptomatic neuroma in patients who have had a lower extremity amputation is 59% and 15%, respectively. Knowledge of their high prevalence may result in better awareness among physicians, in turn providing timely and adequate management.
The first direct catalytic asymmetric α-amination of aldehydes is described herein. α-Unbranched aldehydes react in this novel proline-catalyzed reaction with dialkyl azodicarboxylates to give ...α-amino aldehydes in excellent yields and enantioselectivities.
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