Journal of the American Chemical SocietyDOI: 10.1021/jacs.1c04976

Suryansh Singh, Hanna Lyle, Luca D’Amario, Elena Magnano, Ilya Vinogradov, and Tanja Cuk

https://ift.tt/2WaPDRa

A novel mass spectrometric method for probing the flash chemistry of electrogenerated reactive intermediates was developed based on rapid collision mixing of electrosprayed microdroplets by using a theta-glass capillary. The two individual microchannels of the theta-glass capillary are asymmetrically or symmetrically fabricated with a carbon bipolar electrode to produce intermediates in situ . Microdroplets containing the newly formed intermediates collide with those of the invoked reactants at sub-10 microsecond level, making it a powerful tool for exploring their ultrafast initial transformations. As a proof-of-concept, we present the identification of the key radical cation intermediate in the oxidative dimerization of 8-methyl-1,2,3,4-tetrahydroquinoline and also the first revealment of previously hidden nitrenium ion involved reaction pathway in the C–H/N–H cross-coupling between N,N’-dimethylaniline and phenothiazine.

https://ift.tt/35EPrLf

An open space microfluidic probe has been developed to stably synthesize reactive intermediates in situ for subcellular chemistry. Reactant systems (A, B) mix and react with each other within a chemical reaction microregion (several μm). The continuously produced free radicals can attack cellular compounds within the microregion before quenching, realizing subcellular radical stimulation.

Abstract

Subcellular stimulation by free radicals is crucial for deeper insight of cell behaviors. However, it remains a tough challenge due to the high spatial precision requirement and short life of radicals. Herein, we report a versatile open microfluidic probe for stable generation of free radical and subcellular stimulation. By optimizing parameters, the chemical reaction can be confined in a microregion with a diameter of several μm, and the real‐time produced reactive radicals can attack the desired subcellular region of a single cell. In order to reveal the attacked region, fluorescent cyanine 3 labeled tyramide free radicals are synthesized, and the target microregion on a single cell is successfully stained by the covalent linking reaction between radicals and membrane proteins, which proves the feasibility of our method. We believe this method will open new avenues for short‐lived reactive intermediates stimulation at the single‐cell/sub‐cell level and selective membrane labeling.

https://ift.tt/3a27k8w

Dynamic evolution of active sites and key oxygen intermediate products during the ORR and OER on N‐doped carbon catalysts are monitored experimentally with in situ ATR‐IR spectra. With the assistance of isotopic labeling, the formation of OOH species from O2− (O2−*+H2O→OOH*+OH−) is suggested to be a possible RDS during the ORR process, whereas the generation of O2 from OOH* species is the most possible RDS during the OER process.

Abstract

The recent mechanistic understanding of active sites, adsorbed intermediate products, and rate‐determining steps (RDS) of nitrogen (N)‐modified carbon catalysts in electrocatalytic oxygen reduction (ORR) and oxygen evolution reaction (OER) are still rife with controversy because of the inevitable coexistence of diverse N configurations and the technical limitations for the observation of formed intermediates. Herein, seven kinds of aromatic molecules with designated single N species are used as model structures to investigate the explicit role of each common N group in both ORR and OER. Specifically, dynamic evolution of active sites and key adsorbed intermediate products including O2 (ads), superoxide anion O2−*, and OOH* are monitored with in situ spectroscopy. We propose that the formation of OOH species from O2− (O2−*+H2O→OOH*+OH−) is a possible RDS during the ORR process, whereas the generation of O2 from OOH* species is the most likely RDS during the OER process.

https://ift.tt/38rIJLd

Journal of the American Chemical SocietyDOI: 10.1021/jacs.9b10265

https://ift.tt/2ZZbIQh

Metal-catalyzed acylnitrene transfer reactions are widely proposed to proceed via M(NCOR) intermediates. In their Research Article (DOI: 10.1002/anie.202100668), Chi-Ming Che and co-workers report [Ru(Por)Cl2]-catalyzed highly selective acylnitrene transfer to alkenes, indoles, silyl enol ethers, and C(sp3)−H bonds to afford aziridines/oxazolines, 3-aminoindoles, α-aminoketones, and N-acyl amines, respectively, and also experimental and computational evidence that porphyrin-supported Ru(NCOR) intermediates, which belong to RuV-imido species, are involved in these reactions.

https://ift.tt/2TRgsZc

Experimental studies including ESI-MS, EPR spectroscopy and KIE, and also DFT calculations point to the intermediacy of a porphyrin-supported RuV(NCOR) species in [RuIV(Por)Cl2]-catalyzed C−N bond formation reactions with acyl azides N3COR (up to 99 % yield). The [RuIV(Por)Cl2]/N3COR catalytic method is applicable to various substrates, including alkenes, indoles, silyl enol ethers, and C(sp3)−H bonds.

Abstract

Metal-catalyzed C−N bond formation reactions via acylnitrene transfer have recently attracted much attention, but direct detection of the proposed acylnitrenoid/acylimido M(NCOR) (R=aryl or alkyl) species in these reactions poses a formidable challenge. Herein, we report on Ru(NCOR) intermediates in C−N bond formation catalyzed by [RuIV(Por)Cl2]/N3COR, a catalytic method applicable to aziridine/oxazoline formation from alkenes, amination of substituted indoles, α-amino ketone formation from silyl enol ethers, amination of C(sp3)−H bonds, and functionalization of natural products and carbohydrate derivatives (up to 99 % yield). Experimental studies, including HR-ESI-MS and EPR measurements, coupled with DFT calculations, lend evidence for the formulation of the Ru(NCOR) acylnitrenoids as a RuV-imido species.

https://ift.tt/3geiGdY

Detailed systematic experimental and computational studies on the roles of transmetalating agent, solvent, base and the likely involvement of in situ formed diazoether derivatives challenge the currently accepted mechanism of the Pd‐catalyzed cross‐coupling of aryldiazonium salts.

Abstract

Pd‐catalyzed cross‐coupling reactions of aryl diazonium salts are generally assumed to proceed via cationic PdII intermediates which in turn would be highly reactive in the subsequent transmetalation step. Contrary to this belief, we herein report our observation and rationalization of opposing reactivities of ArN2+ in Suzuki (=effective) and Stille (=ineffective) cross‐couplings in MeOH. Our systematic experimental and computational studies on the roles of transmetalating agent, solvent, base and the likely involvement of in situ formed diazoether derivatives challenge the currently accepted mechanism. Our data suggest that the observed solvent dichotomy is primarily due to PdII‐methoxy intermediates being formed, which are unreactive with arylstannanes, but highly reactive with arylboronic acids, complementing the Suzuki “Pd‐oxy” mechanism with the direct demonstration of transmetalation of a PdII‐alkoxy complex. Lewis acids were found to circumvent this reactivity divergence, promoting efficient couplings regardless of the employed conditions or coupling partners.

https://ift.tt/2MDES51

Journal of the American Chemical SocietyDOI: 10.1021/jacs.0c09317

Henrik Quanz, Bastian Bernhardt, Frederik R. Erb, Marcus A. Bartlett, Wesley D. Allen, and Peter R. Schreiner

https://ift.tt/3phnLoi

The 18‐electron cobalt hydride (R,R)‐(iPrDuPhos)Co(CO)2H has been synthesized. Despite being coordinatively saturated this compound promotes reversible 2,1‐insertion of styrene and catalytic hydrogenation, raising questions as to the mechanism of action of the modified cobalt catalysts.

Abstract

Intermediates relevant to cobalt‐catalyzed alkene hydroformylation have been isolated and evaluated in fundamental organometallic transformations relevant to aldehyde formation. The 18‐electron (R,R)‐(iPrDuPhos)Co(CO)2H has been structurally characterized, and it promotes exclusive hydrogenation of styrene in the presence of 50 bar of H2/CO gas (1:1) at 100 °C. Deuterium‐labeling studies established reversible 2,1‐insertion of styrene into the Co−D bond of (R,R)‐(iPrDuPhos)Co(CO)2D. Whereas rapid β‐hydrogen elimination from cobalt alkyls occurred under an N2 atmosphere, alkylation of (R,R)‐(iPrDuPhos)Co(CO)2Cl in the presence of CO enabled the interception of (R,R)‐(iPrDuPhos)Co(CO)2C(O)CH2CH2Ph, which upon hydrogenolysis under 4 atm H2 produced the corresponding aldehyde and cobalt hydride, demonstrating the feasibility of elementary steps in hydroformylation. Both the hydride and chloride derivatives, (X=H−, Cl−), underwent exchange with free 13CO. Under reduced pressure, (R,R)‐(iPrDuPhos)Co(CO)2Cl underwent CO dissociation to form (R,R)‐(iPrDuPhos)Co(CO)Cl.

https://ift.tt/2wgAb8X

Intermediates relevant to cobalt‐catalyzed alkene hydroformylation have been isolated and evaluated in fundamental organometallic transformations relevant to the catalytic process. Among these, the 18‐electron cobalt carbonyl hydride with a chiral bis(phosphine), ( R , R )‐( iPr DuPhos)Co(CO) 2 H has been structurally characterized. Despite being an analog of rhodium precatalysts widely used in asymmetric hydroformylation, ( R , R )‐( iPr DuPhos)Co(CO) 2 H promoted exclusive hydrogenation of styrene in the presence of 750 psi of H 2 /CO gas (1:1) at 100 ºC. Deuterium labeling studies established reversible 2,1 insertion of styrene into the Co–D bond of ( R , R )‐( iPr DuPhos)Co(CO) 2 D. Whereas rapid β‐H elimination from cobalt alkyls occurred under an atmosphere of N 2 , alkylation of the cobalt chloride ( R , R )‐( iPr DuPhos)Co(CO) 2 Cl in the presence of CO enabled the interception of a cobalt acyl complex, ( R , R )‐( iPr DuPhos)Co(CO) 2 C(O)CH 2 CH 2 Ph. Hydrogenolysis of the cobalt acyl under 4 atm H 2 produced the corresponding aldehyde and cobalt hydride, demonstrating the feasibility of elementary steps in hydroformylation. While the hydride derivative was inert to CO substitution, the π‐donating chloride ligand in ( R , R )‐( iPr DuPhos)Co(CO) 2 Cl underwent rapid CO dissociation (or exchange) to form a tetrahedral, S = 1 complex, ( R , R )‐( iPr DuPhos)Co(CO)Cl.

https://ift.tt/2wgAb8X

I'll start this post off by welcoming you all, if you are a newer player and you've found your way to this thread, I hope you find everything you need here to get started! If you are an older player/veteran to the game, and want to contribute or feel any information in this post is out of date please let me know and I'll do my best to get it back up to date.

If you are looking for an extensive list of guides and resources, scroll down to the bottom of this post!

The first step is diving into the most frequent topic when it comes to Legends of Runeterra and new players, the economy. Legends of Runeterra is a very free to play game, with multiple ways to obtain and use resources to craft cards. While it is very generous, it can feel a tad overwhelming at first. So, we'll take a moment to break down how it all works.

Cards are crafted or purchased using various currencies in game.
Shards - Shards are the most common currency you will come accross, they are represented by a green gem icon. These can be used to craft any card in the game for varying costs.
Wildcards - Wildcards are sorted by rarity and can craft any card of the same rarity. For example, a common wild card will create any common card of your choice. Each rarity is represented by a color, which will be shown in the table below.
Coins - This is the paid currency in Legends of Runeterra, they can be used to purchase cards or cosmetics.

Duplicate Shards - This is how many shards you will receive upon gaining a copy of a card that you already own 3 copies of. Champion and Epic rarity cards have protection, which means upon receiving a 4th copy it will be converted to another random champion or epic card. Once you own every champion/epic card in the game you will start receiving duplicate shards.

So how do we obtain these resources?
The main source will be Capsules and Chests obtained through playing the game. Each chest or capsule in the game has a chance to upgrade to a higher tier upon redemption, if it upgrades it will roll again to see if it upgrades further. This method is repeated for each item in your c

First of all, I want to thank /r/learnprogramming and /r/androiddev. When I had questions you helped me, when I had a bad day - and I had a lot - I read about the journey of people who succeeded in their career change and it kept me motivated.And the mandatory: “Sorry for my English”.

Timeline

- At 28 I didn’t know anything about programming.
- At 30 I got my first job as a developer.
- At 32 I lost my job during the pandemic.
- At 33 I’m launching an app with two friends.

Some advices

• Languages and frameworks are just tools. Learn broad concepts, read a lot of code and learn to search on Google / Stackoverflow.
• I didn’t get my first job because I knew all the new trends, nor that I knew perfectly a language syntax and data structures. I got it because I’m always willing to learn, because I enjoy solving problems, because you can’t be more motivated than I am and because sometimes you are in the right place at the right time. The right mindset will get you the skills, eventually. And that’s what a company should look for in a junior developer. So don’t be too hard on yourself, be patient, have discipline, believe in you and believe in others!

Journey

At 24 I graduated with a master degree in marketing and started to work in advertising in Paris. From the beginning I wasn't really excited about it, it was boring and meaningless. From being bored I went to being unhappy and it started to affect my personal life. At 28 I realised it was time for a change. And because I’m not always the sharpest tool in the shed I quit without any plan. PLEASE DO NOT DO THAT, DON'T QUIT YOUR JOB IF YOU DON'T HAVE A SOLID PLAN OR A JOB OFFER. I had enough savings to live for 1 year without income. When I was younger I thought about programming but I felt it was too complicated for me. Truth is I was really lazy back then so I decided to give it a try.

October 2016

I started to learn HTTP and CSS. I had already learned the basics of the basics a few years ago when I decided to change the colors of a WordPress theme to put my resume on. But I soon realized that I didn't want to create websites, for no specific reason, I just didn't feel like it was my thing.

November 2016

I was still attracted to the idea of being a developer, so I looked for a subreddit about programming and went straight to "Which programming language should I start with?". I told myself "well, I already heard about JAVA, I have an Android phone so let's try that". I star

LINK: https://investors.cloverhealth.com/news-releases/news-release-details/clover-healths-follow-offering-ama

12/17/2021: Hello everyone. We appreciate your patience on hearing from us during the quiet period connected to our follow-on offering (which was due to the fact that our underwriters had 30 days to purchase additional shares). We are more excited than ever in our long-term vision for Clover, with a goal of generating long-term value for shareholders and incredibly positive and massive impact within healthcare.

Before we get into the specific questions that have been asked of us since the launch of the offering, we wanted to provide a general summary of the outcome:

• We raised $300 million in gross proceeds through the offering of our Class A Common Stock.
• We are a technology company that is rapidly growing, and plan to use the proceeds for working capital and general corporate purposes, which includes our continued growth efforts and to have further cushion in the event COVID-19 has a larger impact than we currently expect.
• Over 40 funds invested in our transaction, and we are very pleased with the quality of the investors who bought shares and the fact that several of our existing investors decided to take part and increase their holdings.
• This deal raised our awareness with additional institutional investors. We met with about 30 investors and our banks spoke with about 150 in total. We expect to gain three additional research analysts – Deutsche Bank, SVB Leerink and Canaccord – early next year.

We are very excited entering 2022. We expect another year of strong growth, and we’re progressing on making the Clover Assistant even more powerful and extending its capabilities further, while leveraging our platform to drive impressive operating synergies over time.

Thanks for being on this journey with us.

Vivek & Andrew

Why did Clover do a secondary offering?
It’s typical for high-growth companies to raise capital in multiple rounds over time (especially those that require to scale operations and marketing). At the end of the third quarter, we had approximately $589 million of cash, cash equivalents and investments on our balance sheet, and we raised an additional $300 million in gross proceeds from the offering. One of our primary motivators, since we are a health insurer, is that we have to put aside capital for

I don't want to step on anybody's toes here, but the amount of non-dad jokes here in this subreddit really annoys me. First of all, dad jokes CAN be NSFW, it clearly says so in the sub rules. Secondly, it doesn't automatically make it a dad joke if it's from a conversation between you and your child. Most importantly, the jokes that your CHILDREN tell YOU are not dad jokes. The point of a dad joke is that it's so cheesy only a dad who's trying to be funny would make such a joke. That's it. They are stupid plays on words, lame puns and so on. There has to be a clever pun or wordplay for it to be considered a dad joke.

Again, to all the fellow dads, I apologise if I'm sounding too harsh. But I just needed to get it off my chest.

Do your worst!

I'm surprised it hasn't decade.

For context I'm a Refuse Driver (Garbage man) & today I was on food waste. After I'd tipped I was checking the wagon for any defects when I spotted a lone pea balanced on the lifts.

I said "hey look, an escaPEA"

No one near me but it didn't half make me laugh for a good hour or so!

Edit: I can't believe how much this has blown up. Thank you everyone I've had a blast reading through the replies 😂

It really does, I swear!

There are thousands of options between companies, different coverstocks, reactive vs. non-reactive, pearl, hybrid or solid options, the list goes on and on.

I would like to buy at least an intermediate ball (I'm a beginner but I don't want to buy a beginner ball only to have to replace it in short order) what I can get fitted to my hand that will do more-or-less everything I need. I'll be in bowling alleys with standard oil patterns and am comfortable using a 14 lb. ball. I am not sure what my rev. rate is, but I bowl often enough so if folks know how to figure it out I'm all ears!

TL;DR I'm looking to buy my first bowling ball but need some help figuring out what I should be looking for.

Because she wanted to see the task manager.

Heard they've been doing some shady business.

They’re on standbi

BamBOO!

Welcome to my absurdly long post where I review every game I played this year! Unlike last year, I covered more retro titles this time, and surprisingly played games from four different decades(!).

Note: when I say I “finished” a game, I simply mean I at least completed the main story. I’m not into achievements or 100%ing games.

When I say “preview”, that means I played long enough to understand the mechanics, but didn’t finish the game. I sometimes preview games if I’m interested but not quite sure if I’m ready to commit to a full playthrough.

Without further adieu…

Might and Magic: Book One - Secret of the Inner Sanctum (DOS, 1986)

Status: Preview

Mechanically, the first Might and Magic is a pretty standard dungeon crawler CRPG, but what separates it from other crawlers of its time is its vast open world. From the beginning, the game gives players a lot of freedom, and assuming you can survive the encounters, you can go pretty much anywhere. The presentation is very minimal, with simple graphics depicting tilesets for towns, dungeons and outdoor areas, meaning you’re going to have to use a lot of imagination to fill in the gaps. That being said, portraits for monsters are lovingly rendered, even if they lack any animations. What really surprised me about this game is how user friendly the interface is. Especially for the time it was made. It’s a testament to the game’s design that I was able to figure out most of the controls without reading the manual. I can’t see myself necessarily finishing a game this archaic, but poking around in it out of historical curiosity was fun.

Pool of Radiance (DOS, 1988)

Status: Ongoing

I can see how later D&D CRPGs took cues from PoR; particularly Baldur’s Gate and Icewind Dale. It’s undoubtedly clunky and dated in a number of aspects, but one thing that Pool of Radiance nails is combat. It’s absolutely brilliant.

Which is good, because combat makes up a majority of the gameplay here. It uses a very tactical turn based system that takes into account things like line of sight, terrain, and character speed. It’s difficult to describe just how satisfying it is to win an especially difficult encounter. I just about cheered the first time my party wiped out a particularly nasty group of hobgoblins.

I just wish inventory management wasn’t such a pain. There are five different currencies with their o

Pilot on me!!

Nothing, he was gladiator.

https://preview.redd.it/7w0hffeg8gd71.jpg?width=800&format=pjpg&auto=webp&s=0ed91ac35598c6d98f73fc27f57d6b0804992f05

Bloons TD 6 v27.0 - Update Notes!

Key Features

• New Boss Bloon Event! Face off against the mighty hulk known as Bloonarius the Inflator!
  • In Events intended to run each week, the Boss will appear on a different map to enhance the variety of tactical decisions around economy and placement. Bosses start appearing at Round 40 and the Tier 5 appears at round 120. Each Tier Boss must be defeated within 20 rounds of its appearance or it’s Game Over.
  • Defeat the Tier 5 Normal Boss to unlock the Elite Boss for a whole new level of challenge. We mean it - Elite is bonkers monkey tough. Beating Tier 5 Normal and Elite Bosses award new badges to show off on Player Profile screens. An Elite badge is a true accomplishment - wear them with pride!
  • Boss Events feature a checkpoint save system instead of normal continues, creating a save at the start of each new Boss Tier.
  • Because of downstream Co-op and competitive Leaderboard features we intend to add in future updates, Boss Events can only be played while online.
  • Difficulty Fair Warning - Bosses are designed to be crazy challenging! If you are new to BTD6, make sure you can win most hard modes and really know how to farm well and maximize tower damage before you take on a Boss. Expect defeat. Nay, revel in it - bathe in anguish then emerge smarter, more capable, and with improved tactics that help you get further each time. If you have built up a stockpile of Powers and Insta Monkeys, feel free to use them - they are not required but they are certainly fair game. And, yes, build those Paragons...
• New Paragon Tower Tier!
  • Paragon status granted to Dart Monkey and Boomerang Monkey, unleashing the might of the Apex Plasma Master and the Glaive Dominus!
  • Merge together all three Tier 5 upgrades of one Monkey Tower type to create an ultimate version that combines the powers of all 3 paths and deals incredible bonus damage to Boss Bloons.
  • Paragon Tier has a significant XP cost and can only be unlocked after unlocking the Tier 5 upgrade of all 3 paths.
  • In battle, Paragons gain strength by absorbing the power of all Monkey Towers of that type on the playfield - the greater the number and effectiveness of the Monkey Towers absorbed, the greater the Degree of Paragon you will create! Paragon Degrees start at 1 and reach a maximum Degree of 100.
  • Onc

Christopher Walken

Dad jokes are supposed to be jokes you can tell a kid and they will understand it and find it funny.

This sub is mostly just NSFW puns now.

If it needs a NSFW tag it's not a dad joke. There should just be a NSFW puns subreddit for that.

Edit* I'm not replying any longer and turning off notifications but to all those that say "no one cares", there sure are a lot of you arguing about it. Maybe I'm wrong but you people don't need to be rude about it. If you really don't care, don't comment.

Subcellular stimulation by free radicals is crucial for deeper insight of cell behaviors. However, it remains a tough challenge due to the high spatial precision requirement and short life of radicals. Herein, we report a versatile open microfluidic probe for stable generation of free radical and subcellular stimulation. By optimizing parameters, the chemical reaction can be confined in a microregion with a diameter of several μm, and the real‐time produced reactive radicals can attack the desired subcellular region of a single cell. In order to reveal the attacked region, fluorescent cyanine 3 labeled tyramide free radicals are synthesized, and the target microregion on a single cell is successfully stained by the covalent linking reaction between radicals and membrane proteins, which proves the feasibility of our method. We believe this method will open new avenues for short‐lived reactive intermediates stimulation at the single‐cell/sub‐cell level and selective membrane labeling.

https://ift.tt/3a27k8w

The recent mechanistic understandings including active sites, adsorbed intermediate products and rate‐determining steps (RDS) of  nitrogen ( N ) ‐ modified  carbon catalysts in   electrocatalytic oxygen reduction (ORR) and oxygen evolution reaction  ( OER ) , however, are still rife with controversies  due to the inevitable coexistence of diverse N configurations and the technical limitation for observing  formed   intermediates. In this work, seven kinds of aromatic molecules with designated single N species  are  used as model structures to investigate the explicit role of each common N group in both ORR and OER.  Specifically, dynamic evolution of active sites and key  adsorbed intermediate products including O 2 (ads), superoxide anion O 2 ‐* and OOH*  are  monitored  with  in situ  spectroscopy. We propose that t he formation of OOH species from O 2 ‐ (O 2 ‐+H 2 O→OOH+OH‐) is a possible RDS during the ORR process, whereas the generation of O 2 from OOH* species is the most possible RDS during the OER process.

https://ift.tt/38rIJLd

Metal‐catalyzed C‐N bond formation reactions via acylnitrene transfer have recently attracted much attention, but direct detection of the proposed acylnitrenoid/acylimido M(NCOR) (R = aryl or alkyl) species in these reactions poses a formidable challenge. Herein we report on Ru(NCOR) intermediates in C‐N bond formation catalyzed by [Ru IV (Por)Cl 2 ]/N 3 COR, a catalytic method applicable to aziridine/oxazoline formation from alkenes, amination of substituted indoles, α‐amino ketone formation from silyl enol ethers, amination of C(sp 3 )‐H bonds, and functionalization of natural products and carbohydrate derivatives (up to 99% yield). Experimental studies including HR‐ESI‐MS and EPR measurements, coupled with DFT calculations, lend evidence for the formulation of the Ru(NCOR) acylnitrenoids as a Ru V ‐imido species.

https://ift.tt/3geiGdY

Pd‐catalyzed cross coupling reactions of aryl diazonium salts are generally assumed to proceed via cationic Pd(II) intermediates which in turn would be highly reactive in the subsequent transmetalation step. Contrary to this belief, we herein report our observation and rationalization of opposing reactivities of ArN2+ in Suzuki (= effective) and Stille (= ineffective) cross‐couplings in MeOH. Our systematic experimental and computational studies on the roles of transmetalating agent, solvent, base and the likely involvement of in‐situ formed diazoether derivatives challenge the currently accepted mechanism. Our data suggest that the observed solvent dichotomy is primarily due to Pd(II)‐ methoxy intermediates being formed, which are unreactive with arylstannanes, but highly reactive with arylboronic acids, complementing the Suzuki "Pd‐oxy" mechanism with the direct demonstration of transmetalation of a Pd(II)‐alkoxy complex. Lewis acids were found to circumvent this reactivity divergence, promoting efficient couplings regardless of the employed conditions or coupling partners.

https://ift.tt/2MDES51

Hi - Below is the AMA we just published on our offering. We appreciate your patience and support!

-Clover IR Team

LINK: https://investors.cloverhealth.com/news-releases/news-release-details/clover-healths-follow-offering-ama

12/17/2021: Hello everyone. We appreciate your patience on hearing from us during the quiet period connected to our follow-on offering (which was due to the fact that our underwriters had 30 days to purchase additional shares). We are more excited than ever in our long-term vision for Clover, with a goal of generating long-term value for shareholders and incredibly positive and massive impact within healthcare. Before we get into the specific questions that have been asked of us since the launch of the offering, we wanted to provide a general summary of the outcome:

• We raised $300 million in gross proceeds through the offering of our Class A Common Stock.
• We are a technology company that is rapidly growing, and plan to use the proceeds for working capital and general corporate purposes, which includes our continued growth efforts and to have further cushion in the event COVID-19 has a larger impact than we currently expect.
• Over 40 funds invested in our transaction, and we are very pleased with the quality of the investors who bought shares and the fact that several of our existing investors decided to take part and increase their holdings.
• This deal raised our awareness with additional institutional investors. We met with about 30 investors and our banks spoke with about 150 in total. We expect to gain three additional research analysts – Deutsche Bank, SVB Leerink and Canaccord – early next year.

We are very excited entering 2022. We expect another year of strong growth, and we’re progressing on making the Clover Assistant even more powerful and extending its capabilities further, while leveraging our platform to drive impressive operating synergies over time. Thanks for being on this journey with us. Vivek & Andrew

Why did Clover do a secondary offering? It’s typical for high-growth companies to raise capital in multiple rounds over time (especially those that require to scale operations and marketing). At the end of the third quarter, we had approximately $589 million of cash, cash equivalents and investments on our balance sheet, and we raised an additional $300 million in gross proceeds from th