Organic Chemistry: A Retrosynthetic Approach to a Diverse Field

Ackerman-Biegasiewicz, Laura K.G.; Arias‐Rotondo, Daniela M.; Biegasiewicz, Kyle F.; Elacqua, Elizabeth; Golder, Matthew R.; Kayser, Laure V.; Lamb, Jessica R.; Le, Christine M.; Romero, Nathan A.; Wilkerson-Hill, Sidney M.; Williams, Dwight A.

doi:10.1021/acscentsci.0c01138

Cited by 18 publications

(33 citation statements)

References 37 publications

(63 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Importantly, the same spectral feature is not observed in the absence of protein (Supplemental Figure 11), suggesting further that binding to the protein active site is required for CT complex formation. 10,22 As no reaction is observed with a brominated analog of 1a, we hypothesize that the CT complex forms between flavin and the σ* C-I orbital rather than the π* of the α,unsaturated ester. Mechanistically, excitation of this complex facilitates electron transfer from flavin to substrate, which results in loss of iodide and the formation of an unstabilized alkyl radical, which then cyclizes to form a resonance stabilized α-acyl radical.…”

Section: Graphical Abstractmentioning

confidence: 91%

Photoenzymatic Generation of Unstabilized Alkyl Radicals: An Asymmetric Reductive Cyclization

Clayman

Hyster

2020

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Flavin-dependent 'ene'-reductases (ERED) can generate stabilized alkyl radicals when irradiated with visible light, however, they are not known to form unstabilized radicals. Here, we report an enantioselective radical cyclization using alkyl iodides as precursors to unstabilized nucleophilic radicals. Evidence suggests this species is accessed by photoexcitation of a charge-transfer complex that forms between flavin and substrate within the protein active site. Stereoselective delivery of a hydrogen atom from the flavin semiquinone to the prochiral radical formed after cyclization provides high levels of enantioselectivity across a variety of substrates. Overall, this transformation demonstrates that photoenzymatic catalysis can address long-standing selectivity challenges in the radical literature.

show abstract

Section: Graphical Abstractmentioning

confidence: 91%

Photoenzymatic Generation of Unstabilized Alkyl Radicals: An Asymmetric Reductive Cyclization

Clayman

Hyster

2020

J. Am. Chem. Soc.

View full text Add to dashboard Cite

show abstract

“…Under no circumstance are the criticisms raised by this communication intended to suggest that the affirmative action “Where are they?” finalized just the opposite. In an extremely difficult time, such as that experienced during the current COVID-19 pandemic, 1 − 3 there is a need for a growing engagement of the academic chemistry community in Brazil. 5 , 8 , 9 Additionally, institutional actions of feminine visibility such as “Where are they?” provide mitigation of gender inequality through the dissemination of the trajectories and careers of highly qualified professional scientists in the field of chemistry.…”

Section: A New Equilibrium State Is Possible!mentioning

confidence: 99%

“…On June 4, 2020, the world was still trying to adapt to the terrible effects of the escalating exponential spread of the pandemic contagion of the new Coronavirus SARS-CoV-2 (COVID-19), 1 − 3 as well as watching closely the developments of the outraged racial protests and violent people who called for justice in the face of the brutal murder of African American George Floyd by a white policeman in the United States of America (USA). 3 , 4 In this context of intense social tension, the international scientific community found itself completely perplexed and highly indignant when faced with inconceivably offensive, sexist, racist, and xenophobic statements, 3 written in the essay “‘Organic synthesis—Where now?’ Is 30 years old. A reflection on the current state of affairs”, published online by the prestigious Angewandte Chemie international edition of the German Chemical Society.…”

Section: Introductionmentioning

confidence: 99%

“…), 8 , 9 , 12 due to the adoption of a double working day in which they are divided between didactic activities and the necessary care for the family and the raising of children. 2 , 5 , 8 , 12 , 13 Besides, the COVID-19 pandemic is so far the most emblematic disease of the Anthropocene 1 , 2 , 14 and has the potential to further intensify the high rate of dropout and abandonment of female students 3 , 5 , 15 and other underrepresented minorities in many STEM disciplines, 9 , 10 which in full pandemic when faced with a sexist, nondiversified and noninclusive academic environment, prefer to abandon it, as is observed in the STEM disciplines of the United States of America (USA). 3 , 16…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Impact Assessment of an Affirmative Action to Promote Diversity, Equity, Inclusion, and Respect in Brazilian Chemistry during the COVID-19 Pandemic

Soares

Mello²,

Naegele³

2021

J. Chem. Educ.

View full text Add to dashboard Cite

In December 2019, the institutional affirmative action "Onde elas estaõ?" ("Where are they?") was launched for the mitigation of gender inequality in the STEM disciplines in Brazil, coincidentally in the same period which the first reports of the COVID-19 pandemic appeared in the city of Wuhan, China. Unfortunately, when evaluating the initiative through different approaches belonging to the Diversity, Equity, Inclusion, and Respect (DEIR) theories, the presence of implicit biases and the invisibility of underrepresented minorities was observed. Approximately 77.5% of the female scientists participating in the initiative were white and belonging to the wealthiest regions (75%) and with the greatest contribution to Brazil's Gross Domestic Product (GDP). On the other hand, Black, Indigenous, and Asian female chemists were not identified, nor were female chemists belonging to the North Region (Brazilian Amazon Region). The DEIR practice "Onde elas estaõ?" has an important role in the dissemination of highly qualified Brazilian female chemists and provides an important source of engagement and sense of community for future generations of female students to avoid abandoning STEM subjects. However, adjustments are needed that take into account greater Diversity, Inclusion, Equity, and Respect.

show abstract

“…With the goal of making everyone feel welcome,t he conference encouraged frank conversations,i ncluding open discussion of the challenges that face women and how these can be more pronounced for women of color and those of other marginalized groups.D iversity,e quity,a nd inclusion (DEI) were at the forefront of two workshops.T he first consisted of am oderated discussion of "Organic Chemistry:ARetrosynthetic Approach to aD iverse Field" with the aim of brainstorming actions one can take to promote DEI in the laboratory and workspace. [13] Thesecond workshop equipped participants with tools to address the issue of racism and its intersection with female identity." Allies Help Tu rn the Tide" was geared specifically toward those not part of ag iven marginalized group.P articipants were encouraged to reflect on the various identities they hold and consider how they might leverage their positions at work to amplify voices that may otherwise go unheard.…”

mentioning

confidence: 99%