Podcasts about negishi

  • 13PODCASTS
  • 16EPISODES
  • 34mAVG DURATION
  • ?INFREQUENT EPISODES
  • May 5, 2025LATEST

POPULARITY

20172018201920202021202220232024


Best podcasts about negishi

Latest podcast episodes about negishi

林氏璧孔醫師的新冠病毒討論會
250506 多慶屋 Negishi牛舌都延長了!日本必備優惠券更新 BicCamera黃金周超殺活動

林氏璧孔醫師的新冠病毒討論會

Play Episode Listen Later May 5, 2025 36:23


2025日本旅遊優惠券大平台 https://linshibi.com/?p=20443 雲端硬碟的優惠券已經更新了! https://reurl.cc/r9Ej24 歡迎加入LINE官方帳號 https://line.me/R/ti/p/%40zlc8389z 以下合作已經延長! 多慶屋 JCB卡加優惠券退稅後再12% off https://linshibi.com/?p=30709 Negishi牛舌 每組人可以送一盤迷你勁道牛舌 https://linshibi.com/?p=42950 二木高爾夫 退稅後再10% off https://linshibi.com/?p=45678 池袋太陽城展望台 https://linshibi.com/?p=42962 池袋陽光水族館 https://linshibi.com/?p=31658 BicCamera黃金周活動 https://linshibi.com/?p=20013 去日本用哪張信用卡/電子支付? https://linshibi.com/?p=46124 KKday折扣碼整理 https://linshibi.com/?p=8696 ✨短期折扣碼:MINI5 ✨ 優惠資訊:KKday 日/韓/泰/越迷你團,享 5% 折扣金額無上限! ∙ 使用期限:至 5/31 ∙ 旅遊期限:至 12/31 限台灣會員,每位會員可使用2次。

jcb kkday negishi
Delikt – Wahre Verbrechen aus Österreichs Süden
Mordversuch an Obdachloser gefilmt: Alles für die Likes?

Delikt – Wahre Verbrechen aus Österreichs Süden

Play Episode Listen Later Aug 6, 2024 25:37


Was einer obdachlosen Frau in Kapfenberg widerfahren ist, ist nur schwer zu fassen. Drei Jugendliche (16, 18 und 19) suchen die Frau gezielt auf, urinieren zuerst auf sie, einer nach dem anderen. Als sie sich schützen will, treten sie auf die wehrlose Frau ein. Per Handy werden die brutalen Szenen festgehalten, später wollen die drei vor ihren Freunden damit prahlen. Doch die brutalen Aufnahmen reichen ihnen nicht.Tags darauf kommen sie erneut zum Unterschlupf ihres Opfers, locken die ältere Frau mit Zigaretten heraus. Dann beginnt ihr Martyrium erneut, nur noch brutaler. Völlig enthemmt treten und schlagen sie zu, immer wieder und wieder. Zuletzt stampft einer der drei noch mit dem Fuß mehrfach auf den am Asphalt liegenden Kopf der Frau, bis sie blutend und bewusstlos liegen bleibt.Mit den Videos versuchen die jungen Täter, ihren Freundeskreis zu beeindrucken. Doch zu ihrer Überraschung stoßen sie dabei nicht nur auf Zuspruch und müssen nun befürchten, dass jemand zur Polizei gehen könnte. Sie sprechen Drohungen aus und üben massiven Druck auf ihr Umfeld aus. Monate später kommt schließlich alles ans Licht. Und vor Gericht.Über die Hintergründe dieses unfassbaren Verbrechens, den Gerichtsprozess und die Frage, was in Menschen vorgeht, die zu so etwas fähig sind, spricht delikt-Host David Knes mit Leoben-Redakteur Andreas Schöberl-Negishi.Links: Interview mit Psychiaterin Isabel BögeObdachlosen-Attacke: Nun hat man Filmerin im VisierHohe Strafen: Drei Verurteilungen wegen Mordversuchs

林氏璧孔醫師的新冠病毒討論會
240722 特樂通eSIM每張減100活動開跑 近期優惠券活動整理

林氏璧孔醫師的新冠病毒討論會

Play Episode Listen Later Jul 21, 2024 54:49


日本優惠券大平台和近期活動資訊 https://linshibi.com/?p=20443 1.特樂通的日本eSIM推出了04b讀者的特價! 活動期間:7/22~7/31(10天) 優惠商品:特樂通的日本eSIM,每張現折100元,買幾張就折幾張 下單連結:https://lihi2.com/2u8nJ 優惠折扣碼:04BJP100(結帳前請輸入折扣碼) eSIM新網站不需註冊會員即可購買 注意事項: 下單前請務必確認手機是否為適用機型與版本 QR code 以電子郵件寄出後即無法退費 安裝後若無法使用,請即時聯絡客服,切勿直接刪除eSIM 官方Line客服:@wihoesim 服務時間:週一至週日 9:00-18:00 另外兩間也請參考。大致上我在沖繩的測速結果凱勝最快,DJB暢日卡次之,都會比特樂通的快些。但都堪用。 DJB上網卡 https://djbcard.com/?aid=14081 凱勝的eSIM卡再度下調售價! 網址:https://bit.ly/3Sk4Nvj 2.讀者專用的Klook折扣碼又來了喔! 要從以下指定連結進去才可以使用! 日本首頁 https://reurl.cc/qVMj30 東京飯店: https://reurl.cc/nDXKo8 大阪飯店: https://reurl.cc/gDld0p 折扣碼:04BJULY ⏰即刻起~7/31 23:59

Money 4 Nothing
Karaoke's Personal Pop

Money 4 Nothing

Play Episode Listen Later Apr 26, 2024 59:05


This past March, Shigeichi Negishi passed away at 100. While you might not know his name, you've certainly enjoyed the musical world he helped create. Negishi has long been credited as the inventor of Karaoke—pulling together consumer electronics, post-work drinking culture, and a love of pop tunes into an era-defining mix. A deeper dive, however, makes the story more complex (and honestly more interesting). Negishi was actually just one of a handful of simultaneous inventors. Far from a distinct commercial product, Karaoke might be better understood as the necessary, albeit somewhat-off-key, shadow of the modern music business. To celebrate this legacy, Saxon and Sam dig into one of the most fascinating elements of our contemporary musical…practice? Industry? Culture? Karaoke has a way of blurring all those the lines. And so, in addition to the history, we explore the big questions: What does it mean to imagine yourself a star? Why do we want to perform Katy Perry songs in front of friends and strangers? How has Karaoke's meaning in American culture changed over time? Where does all this fit into the history of folk music—and what does it mean for our social-media future? A first pass, and definitely not a final say. Just hoolllddd onttooo that feeeellinnnnn....   Subscribe to our Newsletter

Fin de Semana
Los sorprendentes beneficios de cantar en un karaoke: "El cerebro se siente seguro"

Fin de Semana

Play Episode Listen Later Apr 6, 2024 8:07


Ana Ibáñez es neurocientífica y desgrana en Fin de Semana el impacto positivo que esta forma de entretenimiento tiene en nuestro organismoHace unos días falleció a los 100 años el inventor del Karaoke, Shigeichi Negishi. Se le ocurrió esta gran idea porque sus compañeros de trabajo le decían que cantaba fatal... Y él pensó, “si yo acompañase mi voz con la base melódica de la canción que estoy cantando, sonaría mucho mejor”... Y así fue cómo nació en el año 1967 uno de los inventos que más felicidad ha generado a muchos... ¿Quién no se ha tronchado cantando a dúo el 'Pega la vuelta' de Pimpinela? Sin duda, el karaoke tiene muchísimos beneficios para el cerebro. Ana Ibáñez ella es neurocientífica, fundadora de los centros de entrenamiento mental Mindstudio y autora del éxito de ventas, 'Sorprende a tu mente' de Editorial Planeta: "Creo que Negishi no era consciente, cuando creó el karaoke, de que hacía algo que tenía tanto impacto positivo a nivel cerebral". "Al cerebro le gusta mucho la música" indicaba la especialista, "y que fluyamos con ella". Explicaba Ana Ibáñez que el cerebro tiende a sentirse seguro, entre otras cosas, cuando comparte con otros algo tan básico como la música: "El mensaje que recibe a tiempo real el cerebro es que no hay peligro, formas parte de este grupo...

林氏璧孔醫師的新冠病毒討論會
231003 新宿高島屋 土產伴手禮 美食推薦 feat.小狸

林氏璧孔醫師的新冠病毒討論會

Play Episode Listen Later Oct 2, 2023 51:00


1.新宿高島屋是新宿南口當年的重大開發案,1996年開幕。JR新宿站新南出口徒步2分就到了新宿高島屋百貨,位於高島屋時代廣場TAKASHIMAYA TIMES SQUARE。這個地上14層、地下1層的巨大複合設施中還有Uniqlo(本館12樓),Nojima電器行(本館11樓),hands(本館南側2~8樓),傢俱店Nitori(南館1~5樓)。 2.免稅櫃台在11樓,可以領取Hello Kitty九五折卡。 3.十二到十四樓三層樓都是餐廳街,有許多餐廳選擇,包括人形町今半壽喜燒,とんかつとん匠豬排,築地玉壽司,燒肉トラジ,赤坂 ふきぬき鰻魚飯,おたる政壽司,名代豬排かつくら京都三条,新宿つな八天婦羅,新宿中村屋,銀座伴助,Negishi(ねぎし)牛舌,京林屋(京はやしや)抹茶甜點等等。 https://www.restaurants-park.jp/ 4.我們選了築地玉壽司,7月26日剛剛開幕的高級干物餐廳:銀座伴助來用餐。這兩者正好看向不同方位的窗景,食物好吃,風景也讚! 5.五樓的高野水果吧タカノフルーツパーラー可以吃到當令的水果聖代。 6.B1食品區介紹:FOUNDRY(ファウンドリー) 水果蛋糕,GRAMERCY NEWYORK(グラマシーニューヨーク) 起司蛋糕,HACCI 1912(ハッチ1912)洋菓子+化妝品,虎ノ門岡埜榮泉 豆大福,坂角総本舖仙貝,虎屋とらや羊羹,小倉山莊仙貝。 延伸閱讀: 日本橋高島屋S.C. 本館是重要文化財 退稅 天然系保養品 牛仔選品櫃 文具 https://linshibi.com/?p=43308 日本橋高島屋本館食品區也很好買! https://linshibi.com/?p=43344 高島屋大阪店 B1地下美食街必吃必買 https://linshibi.com/?p=41805 高島屋京都店 阪急京都河原町站直通 https://linshibi.com/?p=42655 歡迎追蹤林氏璧孔醫師的發聲管道,了解最新的日本旅遊訊息! 我的電子名片 https://lit.link/linshibi 日本優惠券大平台和近期活動資訊 https://linshibi.com/?p=20443 歡迎贊助04b喝咖啡 https://pay.firstory.me/user/linshibi

林氏璧孔醫師的新冠病毒討論會
230723 根岸牛舌Negishi ねぎし 牛肉外還有豬雞的選擇 feat.小狸

林氏璧孔醫師的新冠病毒討論會

Play Episode Listen Later Jul 22, 2023 18:14


根岸牛舌Negishi ねぎし https://www.negishi.co.jp/CN/index.html 第一次來吃很多人都吃過的ねぎし牛舌(根岸,Negishi)。這是一間在新宿歌舞伎町發跡的牛舌連鎖店。和一般仙台系的牛舌店相比,如果有不想,不敢吃牛舌的朋友隨行,就是他有豬肉肉片或豬排,甚至雞肉的選擇!而且想嘗試多種口味的話還可以叫拼盤,可以每一種肉品都能嘗到!我們全家人都覺得還不錯呢! 這個是店內的潛規則:小學生以下(大概12歲以下),店員可能會主動詢問你套餐的醬菜要不要改成果汁喔!當然如果你主動提出,應該也是沒有問題。 「牛たん とろろ 麦めし ねぎし」 主要是在東京的一間店,東京32店舗,橫濱4店舗,千葉1店舗,埼玉1店舗。 https://www.negishi.co.jp/CN/locations.html 延伸閱讀: 東山牛舌 https://linshibi.com/?p=17379 利久牛舌 https://linshibi.com/?p=1611 歡迎追蹤林氏璧孔醫師的發聲管道,了解最新的日本旅遊訊息! 我的電子名片 https://lit.link/linshibi 日本優惠券大平台和近期活動資訊 https://linshibi.com/?p=20443 歡迎贊助04b喝咖啡 https://pay.firstory.me/user/linshibi

cn negishi
Science In-Between
Episode 27: Definitely Not Luke Skywalker

Science In-Between

Play Episode Listen Later Mar 3, 2021 38:42


As part of our on-going discussion of the Cross Cutting Concepts in the NGSS, we examine Scale, Proportion and Quantity in this week's episode. We discuss the challenges with teaching these concepts and provide some solutions as well. Here are some of the resources we share in this episode: Next Generation Science Standards (https://www.nextgenscience.org) Cross Cutting Concepts (pdf download) (https://www.nextgenscience.org/sites/default/files/resource/files/Appendix%20G%20-%20Crosscutting%20Concepts%20FINAL%20edited%204.10.13.pdf) Powers of Ten (https://www.youtube.com/watch?v=0fKBhvDjuy0) Zoom Book by Istvan Banyai (https://www.youtube.com/watch?v=JMhUujrN4iU) We also discuss some research on students' challenge with scale including: Tretter, T.R., Jones, M.G., Andre, T., Negishi, A., & Minogue, J. (2006). Conceptual boundaries and distances: Students’ and experts’ concepts of the scale of scientific phenomena. Journal of Research in Science Teaching, 43 (3), 282–319. Which can be downloaded at: https://onlinelibrary.wiley.com/doi/pdf/10.1002/tea.20123?casatoken=TJTH1B5jXAAAAAA:fW0AYI2ESZkLFLsXBKlG8XkHPott2cPyByYTPQCj5VmuhWBAYRbOAfGYBerLp1U9Y-1NirfqaUqPFbOg In our discussion, we compare how the students' development sense of scale can be compared to science knowledge outlined in A Private Universe (https://www.learner.org/series/a-private-universe/) Need some prompts for talking scale, proportion and quantity with your students? Check out: http://stemteachingtools.org/assets/landscapes/STEM-Teaching-Tool-41-Cross-Cutting-Concepts-Prompts.pdf Things that bring us joy this week: Premier League Soccer (https://www.premierleague.com/) The Flight Attendant on HBOMax (https://www.hbomax.com/grw-fa?utm_id=sa%7c71700000076234780%7c58700006507776317%7cp58828661502&gclid=Cj0KCQiAvvKBBhCXARIsACTePW8zWqNTA6vlZD9hLQB8FkcAGxlKI_umIFjcuxvGCP8Rsnp8m8SkZg8aAgg-EALw_wcB&gclsrc=aw.ds) Intro/Outro Music: Notice of Eviction by Legally Blind (https://freemusicarchive.org/music/Legally_Blind) Production assistance by Enzo Dreon

Art Hounds
Art Hounds: Yuya Negishi's murals animate Twin Cities buildings

Art Hounds

Play Episode Listen Later Jul 9, 2020 5:10


Artist Tuesdae Goldenstarr is a big fan of Yuya Negishi’s murals and other art. Negishi mainly works with a combination of stencils and freestyle; his brightly colored images often feature dragons and other creatures against dramatic backdrops. Negishi just finished a piece at Los Andes Latin Bistro; you can find several of his distinctive murals across the Twin Cities. Side note: He was also part of the team that painted the Bob Dylan mural in downtown Minneapolis. These days, actor Jared Reise heads to the bar almost every night. But don’t worry, it’s entirely COVID-19-safe. Reise has been attending “The Cut-Out Bar,” a nightly streamed event on Facebook and Instagram. Actor Sam Landman prepares himself a white Russian, and picks out a record album for folks to listen to and critique. Reise says generally the music is pretty bad — which makes for great conversations in the chat room, where he and other barflies have bonded over the past three months. Reise says it’s part social hour, part performance piece, and just what he needs to get away from it all at the end of the day. John Sievers of the jazz band “The D’Sievers” thinks you should check out Megan Kleven’s new album “I Am.” Sievers says the album is a musical journey, with nods to rock, folk, Celtic and more. Kleven is performing a CD release concert on Saturday at Chatfield Center for the Arts; if you can’t make it to Chatfield the concert will be available for livestream.

Investor Perspectives Podcast
The appeal of Japan as a destination for international capital looking for safe-haven markets

Investor Perspectives Podcast

Play Episode Listen Later Jun 25, 2020 13:56


Global investors are preparing to double down on Japanese real estate and deploy sizable chunks of the $40 billion of dry powder capital earmarked for Asia Pacific into the country. In this podcast, our host, Art Patnaude, has a dialogue with JLL's Stuart Crow, CEO Capital Markets, Asia Pacific speaking to us from his home office in Singapore and Kenichi Negishi, Head of Capital Markets, Japan, joining us from Tokyo. The topic at hand - Why is Japan set to attract greater volumes of international capital. “Japan will be one of the least impacted markets in Asia Pacific and will probably emerge as one of the more attractive investment destinations for cross-border capital in the second half of 2020,” says Stuart Crow. “Global investors have long desired greater exposure to Japan, and with a slight price correction, there will be greater opportunities.” “Pricing has usually been the main challenge faced by investors as well as tight supply in Tokyo,” explains Kenichi Negishi. “When international investors look at Japan, they see a safe haven and a core investment market within global and regional strategies. They are also looking for stable income, and typically office is one of the sectors that provide a very stable cash flow, which becomes more attractive if there is a price adjustment.” Diversification is a theme that we expect to continue. “We are anticipating global investors to increase allocations to Japan and accelerate plans to look beyond Tokyo into markets like Osaka and Fukuoka,” says Negishi. “Investors view Japan through a more diverse lens when looking into increased exposure, which can also be seen through the growing attraction to emerging asset classes like data centres, logistics, and multifamily”. In the short term, the impact of COVID-19 on Japan's real estate market is expected to be less than the global financial crisis. And despite expectations that transaction volumes for the whole 2020 will register a 25% decrease from the previous year, global investor sentiment towards Japanese real estate is already showing signs of a meaningful shift.

Curiosity Daily
“Rub Some Dirt on It” to Heal Wounds, Funny Memes Can Save Endangered Species, and Space Changes the Shape of Astronauts’ Hearts

Curiosity Daily

Play Episode Listen Later May 28, 2020 10:19


Learn about whether it’s a good idea to rub dirt on your wounds; how funny memes can help save endangered species like the proboscis monkey; and how space travel changes the shape of astronauts’ hearts. When it comes to wounds, science says "rub some dirt on it" might be good advice by Cameron Duke Dillow, C. (2013, May 23). Got A Wound? Science Says Rub Some Dirt In It. Popular Science; Popular Science. https://www.popsci.com/science/article/2013-05/antibacterial-clays-can-kill-antibiotic-resistant-e-coli-and-mrsa/  Juang, L. J., Mazinani, N., Novakowski, S. K., Prowse, E. N. P., Haulena, M., Gailani, D., Lavkulich, L. M., & Kastrup, C. J. (2020). Coagulation factor XII contributes to hemostasis when activated by soil in wounds. Blood Advances, 4(8), 1737–1745. https://doi.org/10.1182/bloodadvances.2019000425 Otto, C. C., & Haydel, S. E. (2013). Exchangeable Ions Are Responsible for the In Vitro Antibacterial Properties of Natural Clay Mixtures. PLoS ONE, 8(5), e64068. https://doi.org/10.1371/journal.pone.0064068 Soil in wounds can help stem deadly bleeding. (2020). EurekAlert! https://www.eurekalert.org/pub_releases/2020-04/uobc-siw042420.php  Funny memes can help people care about unpopular and unappealing species by Kelsey Donk The new Noah’s Ark: beautiful and useful species only. Part 1. Biodiversity conservation issues and priorities. (2011). Biodiversity. https://www.tandfonline.com/doi/full/10.1080/14888386.2011.642663  Lenda, M., Skórka, P., Mazur, B., Sutherland, W., Tryjanowski, P., Moroń, D., Meijaard, E., Possingham, H. P., & Wilson, K. A. (2020). Effects of amusing memes on concern for unappealing species. Conservation Biology. https://doi.org/10.1111/cobi.13523  Proboscis Monkey | National Geographic. (2010, November 9). Nationalgeographic.com. https://www.nationalgeographic.com/animals/mammals/p/proboscis-monkey/  Proboscis monkey meme mentioned: Typowy Polak: Janusz Nosacz - Posts. (2018). Facebook.com. https://www.facebook.com/TypowyPolakJanuszNosacz/posts/1658533764253793/  Space Travel Changes The Shape of Astronauts' Hearts by Haley Otman Study Finds Astronauts’ Hearts Become More Spherical in Space - American College of Cardiology. (2014). American College of Cardiology. https://www.acc.org/about-acc/press-releases/2014/03/29/09/09/may-hearts-in-space  May, C., Borowski, A., Martin, D., Popovic, Z., Negishi, K., Hussan, J. R., Gladding, P., Hunter, P., Iskovitz, I., Kassemi, M., Bungo, M., Levine, B., & Thomas, J. (2014). Affect of Microgravity on Cardiac Shape: Comparison of Pre- and In-Flight Data to Mathematical Modeling. Journal of the American College of Cardiology, 63(12), A1096. https://doi.org/10.1016/s0735-1097(14)61096-2  Subscribe to Curiosity Daily to learn something new every day with Cody Gough and Ashley Hamer. You can also listen to our podcast as part of your Alexa Flash Briefing; Amazon smart speakers users, click/tap “enable” here: https://www.amazon.com/Curiosity-com-Curiosity-Daily-from/dp/B07CP17DJY

Our Food Adventures
Switzerland on a Budget, Kangaroo Testicles and Cheese and Chocolate Factories with Seraina from Lost in Switzerland.com

Our Food Adventures

Play Episode Listen Later Jan 10, 2019 61:12


Our Guest Seraina from LostinSwitzerland.com is a Swiss native who loves showing off her country. Her blog posts help people explore and get lost in Switzerland at a more affordable price. She’s been featured in multiple media outlets about her website and love of Switzerland. If you plan on going, she’s the one who can make your trip amazing! In this episode, Seraina explains how to travel around Zurich, what to do around there while in a budget and where to get the best cheese and chocolate.  What You’ll Learn How to travel around Switzerland the best How to explore Zurich while on a budget What to do if it’s raining in Zurich What to eat in Zurich What factories you should explore in Zurich Where you can purchase alcohol What phrases that will be useful for talking to locals   Spots to Chow  -Crèperie in Aarau and Winterthur -Ässbar -Thai Sunshine in Solothurn -Spiga in Zurich -Negishi in Zurich -Thach -Visaminstation in Solothurn -Gemperli in St. Gallen -Chanh -Dieci Pizza   Things to Do -Appenzell cheese factory -Gruyère cheese factory -Cailler -Emmental cheese factory -Engelberger cheese factory -Kambly Factory   Phrases Hi / Hello - grüezi (You say this to people you're not on first name basis with, like when you're in the street or entering a shop or a restaurant.) Thank you - danke  Please - bitte  I'm lost - Ich habe mich verlaufen. Where's the train station? - Wo ist der Bahnhof? How much does this cost? - Wie viel kostet das? If you want to know more about chocolate factories in Switzerland, go to: https://lostinswitzerland.com/kambly-factory/    If you want to learn more about Seraina and her adventures, visit her website and subscribe! https://lostinswitzerland.com/ Share your thoughts with us! We’d like to hear from you about places you might want to learn more about or even stories about your adventures. Message us through our website OurFoodAdventures.com. Share the show on your Facebook, Instagram or Twitter. Let us know how much you liked the episode with a 5-star rating and what your favorite part was.   Thanks for listening! -Chris and Tiarra

Claycasting
Claycasting #3 - Mika Negishi-Laidlaw

Claycasting

Play Episode Listen Later Feb 24, 2014 103:30


Mika is a Ceramic artist who is currently an Associate Professor at Minnesota State University, Mankato. She sat down with me to catch up about what she has been doing recently at her studio in her home in Mankato, MN. Please check out her work at www.mikanegishilaidlaw.com . And don't forget to subscribe to the podcast in iTunes and rate it if you have the chance. Please help me to spread the word about this podcast and tell you friends. Thank you and Enjoy!

University Communications
Denzel Washington Greets Students at Penn's 2011 Commencement

University Communications

Play Episode Listen Later Jul 11, 2011 2:01


Denzel Washington spoke at the University of Pennsylvania's 2011 Commencement on May 16, 2011. Before the ceremony, he greeted and congratulated students with Penn's President, Dr. Amy Gutmann. Washington emphasized the importance of taking risks: "Taking risks is not about going for a job; it's also about knowing what you know and what you don't know. It's about being open to people and to ideas." Other 2011 Penn honorary degree recipients included Renée C. Fox, the Annenberg Professor Emerita of the Social Sciences at Penn and a pioneer in the field of medical sociology; Mo Ibrahim, the mobile communications entrepreneur who founded Celtel; Nicholas D. Kristof, columnist at The New York Times, and Sheryl WuDunn, senior managing director, Mid-Market Securities, and president of the social investing consultancy, TripleEdge; Ei-ichi Negishi, the recipient of the 2010 Nobel Prize in Chemistry; and Joyce Carol Oates, award-winning author, poet and playwright.

Fakultät für Chemie und Pharmazie - Digitale Hochschulschriften der LMU - Teil 03/06
Verbesserte Darstellung hochfunktionalisierter Zinkorganyle durch direkte Zink-Insertion und deren Anwendung in der Negishi-Kreuzkupplung

Fakultät für Chemie und Pharmazie - Digitale Hochschulschriften der LMU - Teil 03/06

Play Episode Listen Later Dec 17, 2010


Fri, 17 Dec 2010 12:00:00 +0100 https://edoc.ub.uni-muenchen.de/15186/ https://edoc.ub.uni-muenchen.de/15186/1/Malakhov_Vladimir.pdf Malakhov, Vladimir

Fakultät für Chemie und Pharmazie - Digitale Hochschulschriften der LMU - Teil 01/06
Mg- and Zn-Mediated Synthesis of Heterocycles in Solution and on the Solid Phase

Fakultät für Chemie und Pharmazie - Digitale Hochschulschriften der LMU - Teil 01/06

Play Episode Listen Later Sep 24, 2000


This work has focussed on the preparation of functionalized heterocyclic organometallics. In the first part, functionalized zinc derivatives were used due to their high functional group tolerance. Thus various thymine derivatives have been prepared both in solution and on the solid phase. Alternatively, a new route to functionalized heterocyclic Grignard reagents was developed using a low-temperature halogen-magnesium exchange. Ester, amide and nitrile functions are tolerated and the resulting organomagnesium derivatives could be reacted with various electrophiles. Finally, we have attempted to perform low-temperature cross-coupling reactions using these functionalized Grignard reagents. 5.1- Synthesis of thymine derivatives Zincated thymine derivative 2 was prepared by zinc insertion from the corresponding bromide 4, readily available in four steps from uracil. Negishi cross-coupling reactions were then performed using zinc reagent 2 and various aryl iodides. N N O O Bn Bn 4 Br HN N H O O N N O O Bn Bn 2 ZnBr Ar - I Pd(dba)2 (2.5 mol %) N N O O tfp (5 mol %) THF, 25 °C, 12 h Bn Bn Ar 3a-j: 62-95 % THF, 0 °C Zn* Scheme 67. Preparation of thymine derivatives 3a-j using a Negishi cross-coupling reaction. Resin-attached aryl iodides were also suitable substrates and solid phase synthesis of thymine derivatives could be performed with high HPLC-purities (89-93 %). X O I N N O O Bn Bn X = O, NH R 8 (10 equiv) N N O O Pd(dba)2 (5 mol %) tfp (10 mol %) THF, 25 °C, 48 h Bn Bn R = CO2H, CONH2 ZnBr 2) TFA 1) 89-93 % HPLC purity Scheme 68. Solid phase synthesis of thymine derivatives. 5.2- Synthesis of functionalized heterocyclic derivatives using a low temperature halogen-magnesium exchange • Synthesis of pyridine derivatives Functionalized pyridinyl Grignard reagents were prepared using a low temperature iodinemagnesium exchange and trapped with electrophiles. Functional groups such as ester, amide or nitrile functions are tolerated in this process. N I FG 1) i-PrMgBr -40 °C 2) E+ N E FG 50-92 % FG = Br, CONR2, CN, CO2R etc. Scheme 69. Preparation of functionalised pyridines using a low temperature iodine-magnesium exchange. The bromine-magnesium exchange is less general than the iodine magnesium-exchange and electron withdrawing groups are often necessary to accelerate the exchange reaction. However, 2-bromo and 3-bromopyridine were suitable substrates due to the π deficient character of these heterocycles. N Br 1) i-PrMgBr THF, rt, 6 h 2) E+ N E 72-75 % Scheme 70. Preparation of pyridine derivatives using a bromine-magnesium exchange. • Synthesis of thiazole and thiophene derivatives A low temperature bromine-magnesium exchange was then used in the synthesis of functionalized thiazole and thiophene derivatives. N S Br OEt O Br 1) i-PrMgBr THF, -78 °C N S Br OEt O E 2) E+ S Br Br CO2Et 1) i-PrMgBr -40 °C, 0.5 h 2) S Br CO2Et 1) i-PrMgBr -40 °C, 0.5 h 2) E+ S E E CO2Et S Br Br EtO2C 1) i-PrMgBr -40 °C, 0.5 h 2) E+ S E Br EtO2C 58-81 % 68-88 % 74 % 62-71 % Br CuCN cat. Scheme 71. Preparation of thiazole and thiophene derivatives using a bromine-magnesium exchange. • Synthesis of dihydrobenzofurans and tetrahydrobenzazepines An access to dihydrobenzofurans, benzolactams and tetrahydrobenzazepines was developed using arylmagnesium reagents bearing an o-chloromethyl group. Cl MgBr CO2Et Br 83 % CuCN 2 LiCl cat. . Cl CO2Et RNH2 reflux, 24 h K2CO3, THF N CO2Et R Cl I 1) i-PrMgBr (1.0 equiv) THF -10 °C, 1.5 h 2) RCHO, -10 °C, 1 h then reflux, 12 h O R 55-94 % 54-75 % X = H, CO2Me NPh X 1) i-PrMgBr (1.0 equiv) THF -10 °C, 1.5 h 2) PhN=C=O O X = H, 96 % X = CO2Me, 75 % Scheme 72. Preparation of dihydrobenzofurans and tetrahydrobenzazepines using a low temperature iodine-magnesium exchange. • Low-temperature halogen-magnesium exchange on the solid phase The low-temperature halogen-magnesium exchange could also be performed on the solid phase using an excess of i-PrMgBr and was applied to the synthesis of various thiophene derivatives. 2) E+ 1) i-PrMgBr (10 equiv) THF, -40 °C 3) TFA S E O HO S O O Br 83-99 % HPLC-purity Scheme 73. Solid phase synthesis of thiophene derivatives using a low temperature brominemagnesium exchange.