RAF는이 작품의 지원 국립 과학 재단 (National Science Foundation) (CHE-0844946)을 감사드립니다.

1. SMI 2 합성 (0.1 M) <ol><li> 불꽃은 50 ML 둥근 바닥 플라스크를 건조 및 아르곤로 플러시. 저어 바를 추가하고 septa와 술병을 다룹니다. 사마륨 금속 (0.2 g, 1.3 mmol)을 무게 다시 아르곤과 술병를 플러싱, 플라스크에 추가 할 수 있습니다. </li><li> 요오드 결정 (0.254 g, 2.0 mmol)에 이어 10 ML 건조하고 철저하게 degassed tetrahydrofuran (THF)을 추가합니다. 심장을 통해 아르곤 풍선을 추가,이 반응에 아르곤 분위기가 긍정적 인 압력을 유지합니다. </li><li> 3 시간 이상 실온에서 적극적으로 솔루션을 저어. SMI 2가 생성되는대로 솔루션은 색깔 변화의 다양한 통과, 오렌지는 노란색 (45 분), 결국 파란색으로 변 녹색 (1 시간)이 나타납니다. </li><li> 최종 해군 블루 색상은 단독으로 이온화 사마륨가 형성되었다는 표시입니다. 전체 변환을 보장하기 위해 합성에 SMI 2 사용하기 전에 적어도 3 시간 동안 솔루션을 젓는다. </li></ol> 2. 사marium Barbier 반응 - 헥사 메틸 포스 포르 아미드 (HMPA) 추가 <ol><li> SMI 2 HMPA 복잡한을 만들려면, 아르곤 아래에있는 신선하게 조리 된 SMI 2 (10 ML, 0.1 M, 1.0 mmol) 걸릴 및 아르곤 아래 주사기, dropwise를 통해 HMPA의 1.75 ML (EQUIV 10., 10 mmol)을 추가합니다. 깊은 보라색 색상 양식. </li><li> 이와는 별도로 아르곤, 추가 iodododecane (0.45 mmol, 110 μl), 3 pentanone (0.45 mmol, 48 μl)와 건조 THF 2 ML 아래 깨끗하고 건조한 유리 병 인치 </li><li> SMI 2 / HMPA 복잡한 dropwise 기판 솔루션 혼합물을 추가합니다. </li><li> 감동의 5 분 이내에, 보라색 색상은 반응의 끝을 나타내는 구름보고 시작합니다. </li><li> 반응이 완료되면을 잃게하는 공기에 대한 해결책을 폭로, 노란색으로 색상 추가 변경 작업을 감동시. </li><li> 반응은 다음 포화 수성 염화 암모늄과 세정에 의해 작동된다. 분리 깔때기에 솔루션을 추가하고 디 에틸 에테르를 (5 ML)를 추가합니다. 활발한 흔들림 제거 후상단 유기 층 더 디 에틸 에테르를 추가합니다. 수성 레이어에서 두 번 추출하고 유기 레이어의 모든 조화를 이루고 있습니다. </li><li> 수성 나트륨 thiosulfate의 포화 용액으로 유기 층을 씻으십시오. 물 한 후 소금물로 최종 세척과 세척을 한 다음 아래 수성 레이어를 제거합니다. 상단 유기 층을 확보하고 솔루션에 물 존재의 마지막 금액을 만끽하기 위해 황산 마그네슘을 추가합니다. </li><li> 초과 HMPA를 제거하기 위해 Florisil의 플러그인을 통해 솔루션을 전달합니다. </li><li> Barbier 제품을 얻기 위해 회전 증발기에 솔루션을 집중. 이 제품은 질량 분석기로 분석해 및 1 H NMR에 의해 확인되었다. 23 </li></ol> 3. 사마륨 Barbier 반응 - 니켈 (acac) 2 촉매 <ol><li> 니켈 (acac) 2 (1 몰의 %, 0.01 mmol, 0.0026 g)을 무게 및 아르곤 아래 degassed THF 3 ML을 포함하는 깨끗하고 건조한 유리 병에 추가 할 수 있습니다. 신선하게 조리 된 s에 주사기를 통해 니켈 (acac) 2 솔루션을 추가0.1 M SMI 2 (1.0 mmol, 10 ML)의 olution. </li><li> 이와는 별도로 아르곤, 추가 iodododecane (0.45 mmol, 110 μl), 3 pentanone (0.45 mmol, 48 μl)와 건조 THF 2 ML 아래 깨끗하고 건조한 유리 병 인치 </li><li> SMI 2 / 니켈의 혼합물로 dropwise 기판 솔루션을 추가합니다. </li><li> 감동의 십오분 이내에, 푸른 색은 반응의 끝을 나타내는 노란색 - 녹색 색상을 형성하는 분산됩니다. </li><li> 반응이 완료되면을 잃게하는 공기에 대한 해결책을 폭로, 노란색으로 색상 추가 변경 작업을 감동시. 0.1 M AQ로 세척하여 반응을 작업 할 수 있습니다. 염산 산 (3 ML). 분리 깔때기에 솔루션을 추가하고 디 에틸 에테르를 (5 ML)를 추가합니다. </li><li> 나트륨 thiosulfate, 물, 염수의 수용액과 이전에 설명한 프로토콜, 황산 마그네슘 이상 후 건조를 사용하여 유기 층을 씻으십시오. Barbier 제품을 확보 할 수있는 솔루션을 집중. 이 제품은 질량 분석기로 분석해 및 1 H NMR에 의해 식별 할 수 있습니다. 28 </s까지&gt; </li></ol>

<ol>
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관심 없음 충돌이 선언 없습니다.

가장 일반적인 첨가제의 두를 사용하여 SMI 두 솔루션과 유기 합성에서의 응용 프로그램을 생성하기위한 간단한 절차를 여기에 제공됩니다. 두 예제는 미세 조정 SMI (2)의 반응에 반응 기계론의 이해의 중요성을 묘사 설명했다. 반응 메커니즘의 underpinning 지식은 반응의 요구에 따라 합성 화학자에 의해 적응이 시약의 사용이 가능합니다. 이 단일 전자 균질 reductant은 처리가 용이​​하며 상용 소스에서 구입하실 수 있습니다. 위의 프로토콜 불활성 조건 하에서 완료되면 바로 앞으로이지만, 일반적인 문제 해결 절차의 일부는 다음과 같습니다 (A) SM 금속 공기에 장시간 노출을 가지고있는 경우 (B)는이 수 THF가 제대로 degassed 건조되어 있는지 확인 레이어 이외의 산화, 깨끗한 금속 표면을 노출 할 수있는 절구와 pestal으로 금속을 부러 (C)불꽃 - 건조 아르곤 아래의 모든 유리와 시원한는 (D)가 나중에 금속과 상호 작용하는 표시 되었기 때문에 아르곤이, 질소으로 불활성 분위기를 선호합니다 (E) SM-금속 초과의 존재는 SMI의 농도를 유지하는 데 도움이 요오드 결정 2, (F) resublime.

<table border="1"><tbody><tr><td> 시약의 이름 </td><td> 회사 </td><td> 카탈로그 번호 </td><td> 코멘트 (선택 사항) </td></tr><tr><td> 사마륨 금속 </td><td> Acros </td><td> 29478-0100 </td><td> -40 메쉬, 99.9 % (금속 기준) </td></tr><tr><td> THF </td><td> OmniSolv </td><td> TX0282-1 </td><td> 혁신적인 기술 용매 정화 시스템을 통해 정화. 또는 그것은 무료 - 펌프 - 해동 방법을 통해 degassed 할 수 있습니다 </td></tr><tr><td> 요오드 </td><td> 알파 Aesar </td><td> 41955-22 </td><td> Resublimed 결정, 99.8 % </td></tr><tr><td> Iodododecane </td><td> Acros </td><td> 25009-0250 </td><td> 98% </td></tr><tr><td> 3 pentanone </td><td> 알파 Aesar </td><td> AAA15297-AE </td><td> 99% </td></tr><tr><td> HMPA </td><td> Alderich </td><td> H11602 </td><td> 98%, 아르곤에서 카오에서 증류 </td></tr><tr><td> NiI 2 </td><td> 알파 Aesar </td><td> 22,893 </td><td> 99.5 % (금속 기준) </td></tr></tbody></table>

preparation and use of samarium diiodide (smi2) in organic synthesis: the mechanistic role of hmpa and ni(ii) salts in the samarium barbier reaction

처음에 비의 시약으로 간주하지만, SMI 2 합성 유기 화학자를위한 공통의 도구가되었습니다. SMI 2 THF에 사마륨 금속 분자 요오드의 추가를 통해 생성됩니다. 1,2-3는 그것은 온화하고 선택적 단일 전자 reductant이고 기능성이 CC를 포함 감소의 다양한 시작하는 능력의 결과이다 본드를 형성 및 계단식이나 연속 반응. SMI 2 sulfoxides와 sulfones, phosphine 산화물, epoxides, 알킬 및 아릴 할로겐, carbonyls 및 복합 더블 채권 등의 기능 그룹의 다양한 줄일 수 있습니다. SMI-2-매개 반응의 매혹적인 기능 2-12 하나의 기능입니다 cosolvents 또는 첨가제의 선택 사용을 통해 반응의 결과를 조작. 대부분의 경우, 첨가제 감소의 속도와 화학 또는 stereoselectivity 반응을 제어에 필수적입니다. 13-14 첨가제의 공동mmonly SMI 2의 반응성이 세 가지 주요 그룹으로 분류 할 수 있습니다 미세 조정에 활용 : (1) 루이스 기지 (HMPA 다른 전자 - 기증자 리간드, 킬레이트 화 에테르 등), (2) 양자 소스 (알코올, 물 등 ), 그리고 (3) 무기 첨가제 (니켈 (acac) 2, FeCl 3 등). 3 SMI 2 반응의 메커니즘과 첨가제의 역할을 이해하는 것은 유기 합성의 시약의 전체 잠재력 활용을 할 수 있습니다. 이 반응의 HMPA과 니켈 (II) : SM-Barbier 반응은 합성 중요성과 일반적인 두 가지 첨가제의 기계론의 역할을 설명하도록 선택합니다. SM-Barbier 반응은 알킬 할로겐화물, 카르 보닐, 그리고 SM의 reductant이 한 냄비에 동시에 혼합되어 있다는 유일한 차이점과 전통 Grignard 반응과 유사합니다. 커플 링 파트너의 범위 SM-매개 Barbier 반응의 1,15 예 보고되었으며, 1,3,7,10,12 및 UT되었습니다대형 자연 제품의 합성의 핵심 단계에 ilized. SMI 두 반응에 대한 첨가제의 효과에 16,17 이전 연구 HMPA는보다 강력한 생산, 사마륨 금속 센터로 조정하여 SMI (2)의 감소 가능성을 향상하는 것으로 나타났습니다, 13-14,18는 sterically reductant 19-21을 encumbered와 SM-Barbier 반응에서 다음 본드 - 성형 이벤트를 촉진 후 전자 - 전송 단계에서 중요한 역할. 22 게임을 경우에, HMPA가 추가로 알킬 할로겐화물을 활성화 보여왔다 사전 평형 단계에서 복잡한을 형성하여. 23 니켈 (II) 염은 SM-매개 변환에 자주 사용되는 촉매 첨가제입니다. 성공을위한되지만 중요한 24-27, 니켈 (II)의 기계론의 역할이 반응에 알 수 없습니다. 최근에는 SMI 2 니켈 (0) 니켈 (II)을 감소하는 것으로 나타되었고, 반응 후 organome을 통해 수행됩니다tallic 니켈 (0) 화학. 28 이러한 기계론의 연구는 동일한 Barbier 제품이 획득되어 있지만, SMI 두 반응에서 다른 첨가제의 사용이 크게 반응의 기계론의 경로를 변경하는 강조 표시합니다. 이 SMI를 실행하기위한 프로토콜은 2 시작 반응이 설명되어 있습니다.

그림 1은 사마륨 Barbier 반응을 보여줍니다. 노 첨가제와 SM-매개 반응은 72 시간 정도 소요되며 나머지되는 출발 물질로 원하는 제품의 69 % 항복. 10 인 이상 EQUIV의 추가가 있습니다. HMPA의 반응이 몇 분 내에 거의 양적 및 완료. 1 몰 % 니켈 (acac) 2의 추가와 함께 15,23, 반응은 97 %의 수율과 함께 15 분 내 완료됩니다. 28 (HMPA) 4 - HMPA는 SMI 2 cosolvent displaces SMI 2를 형성 할 수있는 조정 THF가 추가합니다. 더 많은 HMPA (EQUIV 6-10.)의 추가로 요오드화물 이온은 외부 영역 (그림 2)에 변위되어 있습니다. 19-21 기계론의 연구는 HMPA은 SM-Barbier 반응에 사용되는 때 cosolvent도 상호 작용을 나타냅니다 알킬 할로겐 기판을 활성화, 탄소 할로겐 결합을 elongates 복잡한을 형성와pecies는 SM의 감소 (그림 3)에 더 취약하고. HMPA, HMPA과 SM-Barbier 반응에 대한 메커니즘의 역할이 자세한 이해를 통해 (그림 4) 제안되었다. 23 미리 평형 단계에서 형성 알킬 할라이드-HMPA 복잡한는 SM / HMPA에 의해 감소를 형성하기 위해 단계를 결정 속도의 급진적. 급진적 인은 카르 보닐이 있으며 protonation시 커플이 최종 제품을 산출 organosamarium 종을 형성하기 위해 더욱 감소를 겪. 니켈 (II) 첨가제의 경우에는 SMI 2 처음 우선적으로 기판 중 하나의 환원 이상의 니켈 (0) 니켈 (II)을 줄일 수 있습니다. 운동과 기계론의 연구를 바탕으로 다음과 같은 메커니즘은 (그림 5) 제안되었다. organonickel 종을 형성 알킬 할로겐화물 채권에 28 SMI 2로 감소 후, 수용성 니켈 (0) 종 삽입. SM의 높은 oxophilic 자연 (III)에 의해 구동<html> 돌아 촉매 사이클에 organosamarium 중간 자료 니켈 (II)를 형성 할 수 transmetallation. 그런 다음 organosamarium 카르 보닐과 연인, protonation시 원하는 고등 술을 형성한다. 그것은 또한 니켈 (0) 나노 입자가 니켈의 SM-매개 감소 (II)를 통해 형성되는 것이 관찰되었다 그러나 이러한 입자가 운영 중지 및 촉매의 비활성화의 소스가된다는 것을 발견했다. <img alt="그림 1" fo:content-width="4in" fo:src="/files/ftp_upload/4323/4323fig1highres.jpg" src="/files/ftp_upload/4323/4323fig1.jpg" /> iodododecane 및 3 pentanone과 그림 1. 사마륨 Barbier 반응. <img alt="그림 2" fo:content-width="4in" fo:src="/files/ftp_upload/4323/4323fig2highres.jpg" src="/files/ftp_upload/4323/4323fig2.jpg" /> 그림 2. SMI 2 HMPA 단지. ontent &quot;강한 : 유지 - together.within 페이지 =&quot;항상 &quot;&gt; <img alt="그림 3" fo:content-width="3.5in" fo:src="/files/ftp_upload/4323/4323fig3highres.jpg" src="/files/ftp_upload/4323/4323fig3.jpg" /> 그림 3. HMPA 및 알킬 요오드화물 복합. <img alt="그림 4" fo:content-width="4.5in" fo:src="/files/ftp_upload/4323/4323fig4highres.jpg" src="/files/ftp_upload/4323/4323fig4.jpg" /> 그림 4. 초과 HMPA과 사마륨 Barbier 반응에 대한 제안 메커니즘. <img alt="그림 5" fo:content-width="4in" fo:src="/files/ftp_upload/4323/4323fig5highres.jpg" src="/files/ftp_upload/4323/4323fig5.jpg" /> 그림 5. 촉매 니켈 (II)를 포함 사마륨 Barbier 반응에 제안 된 메커니즘.

Watch this Scientific Journal Video about Preparation and Use of Samarium Diiodide SmI2 in Organic Synthesis: The Mechanistic Role of HMPA and NiII Salts in the Samarium Barbier Reaction at JoVE.com

Preparation and Use of Samarium Diiodide SmI2 in Organic Synthesis: The Mechanistic Role of HMPA and NiII Salts in the Samarium Barbier Reaction

사마륨 diiodide의 준비를위한 간단한 절차 (SMI<sub&gt; 2</sub&gt;) THF에이 설명되어 있습니다. (acac) 즉 헥사 메틸 포스 포르 아미드 (HMPA)와 니켈 두 가지 첨가제의 역할<sub&gt; 2</sub&gt; SM에 매개 반응은 SM-Barbier 반응에 증명하고 있습니다.

준비와 사마륨 Diiodide 이용 (SMI<sub&gt; 2</sub&gt;) 유기 합성의 : 사마륨 Barbier 반응에 HMPA과 니켈 (II) 소금의 기계론의 역할

Although initially considered an esoteric reagent, SmI2 has become a common tool for synthetic organic chemists. SmI2 is generated through the addition of ...

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Preparation and Use of Samarium Diiodide (SmI2) in Organic Synthesis: The Mechanistic Role of HMPA and Ni(II) Salts in the Samarium Barbier Reaction

32.8K 조회수.  Lehigh University. 사마륨 diiodide의 준비를위한 간단한 절차 (SMI 2) THF에이 설명되어 있습니다. (acac) 즉 헥사 메틸 포스 포르 아미드 (HMPA)와 니켈 두 가지 첨가제의 역할 2 SM에 매개 반응은 SM-Barbier 반응에 증명하고 있습니다.

비디오: Preparation and Use of Samarium Diiodide SmI2 in Organic Synthesis: The Mechanistic Role of HMPA and NiII Salts in the Samarium Barbier Reaction

Split-and-pool Synthesis and Characterization of Peptide Tertiary Amide Library

Peptidomimetics are great sources of protein ligands. The oligomeric nature of these compounds enables us to access large synthetic libraries on solid phase by using combinatorial chemistry. One of the most well studied classes of peptidomimetics is peptoids. Peptoids are easy to synthesize and have been shown to be proteolysis-resistant and cell-permeable. Over the past decade, many useful protein ligands have been identified through screening of peptoid libraries. However, most of the ligands identified from peptoid libraries do not display high affinity, with rare exceptions. This may be due, in part, to the lack of chiral centers and conformational constraints in peptoid molecules. Recently, we described a new synthetic route to access peptide tertiary amides (PTAs). PTAs are a superfamily of peptidomimetics that include but are not limited to peptides, peptoids and N-methylated peptides. With side chains on both &#945;-carbon and main chain nitrogen atoms, the conformation of these molecules are greatly constrained by sterical hindrance and allylic 1,3 strain. (Figure 1) Our study suggests that these PTA molecules are highly structured in solution and can be used to identify protein ligands. We believe that these molecules can be a future source of high-affinity protein ligands. Here we describe the synthetic method combining the power of both split-and-pool and sub-monomer strategies to synthesize a sample one-bead one-compound (OBOC) library of PTAs.

Peptide tertiary amides (PTAs) are a superfamily of peptidomimetics that include but are not limited to peptides, peptoids and N-methylated peptides. Here we describe a synthetic method which combines&#160;both split-and-pool and sub-monomer strategies to synthesize a one-bead one-compound library of PTAs.

분할 및 풀 합성 펩타이드 급 아미드 도서관의 특성

Peptidomimetics are great sources of protein ligands. The oligomeric nature of these compounds enables us to access large synthetic libraries on solid ...

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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. Isonicotinic acid, or its derivatives, are coupled to variable length diaminoalkane chains under an inert atmosphere in anhydrous DMF or DMSO with the use of a weak base, triethylamine, and a coupling agent, 1-propylphosphonic anhydride. The products precipitate from solution upon formation or can be precipitated by the addition of water. If desired, the ligands can be further purified by recrystallization from hot water. Dinuclear platinum complex synthesis using the bispyridine ligands is done in hot water using transplatin. The most informative of the chemical characterization techniques to determine the structure and gross purity of both the bispyridine ligands and the final platinum complexes is 1H NMR with particular analysis of the aromatic region of the spectra (7-9 ppm). The platinum complexes have potential application as anticancer agents and the synthesis method can be modified to produce trinuclear and other multinuclear complexes with different hydrogen bonding functionality in the bridging ligand.

This protocol describes the use of amide coupling reactions of isonicotinic acid and diaminoalkanes to form bridging ligands suitable for use in the synthesis of multinuclear platinum complexes, which combine aspects of the anticancer drugs BBR3464 and picoplatin.

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Synthesis and Characterization of Functionalized Metal-organic Frameworks

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.

Synthesis, activation, and characterization of intentionally designed metal-organic framework materials is challenging, especially when building blocks are incompatible or unwanted polymorphs are thermodynamically favored over desired forms. We describe how applications of solvent-assisted linker exchange, powder X-ray diffraction in capillaries and activation via supercritical CO2 drying, can address some of these challenges.

기능화의 합성 및 특성 금속 - 유기 프레임 워크

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and ...

Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus

Here we present a protocol for the synthesis of two distinct carbonyl-decorated carbenes. Both carbenes can be prepared using nearly identical procedures in multi-gram scale quantities. The goal of this manuscript is to clearly detail how to handle and prepare these unique carbenes such that a synthetic chemist of any skill level can work with them. The two carbenes described are a diamidocarbene (DAC, carbene 1) and a monoamidoaminocarbene (MAAC 2). These carbenes are highly electron-deficient and as such display reactivity profiles that are atypical of more traditional N-heterocyclic carbenes. Additionally, these two carbenes only differ in their electrophilic character and not their steric parameters, making them ideal for studying how carbene electronics influence reactivity. To demonstrate this phenomenon, we are also describing the activation of white phosphorus (P4) using these carbenes. Depending on the carbene used, two very different phosphorus-containing compounds can be isolated. When the DAC 1 is used, a tris(phosphaalkenyl)phosphane can be isolated as the exclusive product. Remarkably however, when MAAC 2 is added to P4 under identical reaction conditions, an unexpected carbene-supported P8&#160;allotrope of phosphorus is isolated exclusively. Mechanistic studies demonstrate that this carbene-supported P8allotrope forms via a [2+2] cycloaddition dimerization of a transient diphosphene which has been trapped by treatment with 2,3-dimethyl-1,3-butadiene.

Here, we present a protocol for the synthesis of two carbonyl-decorated carbenes. The protocol makes these interesting compounds readily available to chemists of all skill levels. In addition to the synthesis of these two carbenes, their use in the activation of white phosphorus is also described.

화이트 인의 활성화에 카르 보닐 장식 카르 벤의 제조 및 사용

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Ynones are a valuable functional group and building block in organic synthesis. Ynones serve as a precursor to many important organic functional groups and scaffolds. Traditional methods for the preparation of ynones are associated with drawbacks including harsh conditions, multiple purification steps, and the presence of unwanted byproducts. An alternative method for the straightforward preparation of ynones from acyl chlorides and potassium alkynyltrifluoroborate salts is described herein. The adoption of organotrifluoroborate salts as an alternative to organometallic reagents for the formation of new carbon-carbon bonds has a number of advantages. Potassium organotrifluoroborate salts are shelf stable, have good functional group tolerance, low toxicity, and a wide variety are straightforward to prepare. The title reaction proceeds rapidly at ambient temperature in the presence of a Lewis acid without the exclusion of air and moisture. Fair to excellent yields may be obtained via reaction of various aryl and alkyl acid chlorides with alkynyltrifluoroborate salts in the presence of boron trichloride.

The goal of this manuscript is to demonstrate a straightforward method for the preparation of ynones from acyl chloride and potassium alkynyltrifluoroborate salt starting materials. The one-pot reaction proceeds rapidly in the presence of boron trichloride without exclusion of air and moisture.

아실 염화물과 칼륨 Alkynyltrifluoroborate 소금에서 Ynones의 금속이 합성

Ynones are a valuable functional group and building block in organic synthesis. Ynones serve as a precursor to many important organic functional groups ...

Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate

This paper describes the synthesis and peroxide-modification of nanosize monosodium titanate (nMST), along with an ion-exchange reaction to load the material with Au(III) ions. The synthesis method was derived from a sol-gel process used to produce micron-sized monosodium titanate (MST), with several key modifications, including altering reagent concentrations, omitting a particle seed step, and introducing a non-ionic surfactant to facilitate control of particle formation and growth. The resultant nMST material exhibits spherical-shaped particle morphology with a monodisperse distribution of particle diameters in the range from 100 to 150&#160;nm. The nMST material was found to have a Brunauer-Emmett-Teller (BET) surface area of 285 m2g-1, which is more than an order of magnitude higher than the micron-sized MST. The isoelectric point of the nMST measured 3.34 pH units, which is a pH unit lower than that measured for the micron-size MST. The nMST material was found to serve as an effective ion exchanger under weakly acidic conditions for the preparation of an Au(III)-exchange nanotitanate. In addition, the formation of the corresponding peroxotitanate was demonstrated by reaction of the nMST with hydrogen peroxide.

The surfactant mediated sol-gel synthesis of nanosized monosodium titanate is described, along with preparation of the corresponding peroxide modified material. An ion-exchange reaction with Au(III) is also presented.

This paper describes the synthesis and peroxide-modification of nanosize monosodium titanate (nMST), along with an ion-exchange reaction to load the ...

Synthesis and Characterization of Supramolecular Colloids

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical properties for applications in photonics, drug delivery and coating technology. Here we present a new family of colloidal building blocks, coined supramolecular colloids, whose self-assembly is controlled through surface-functionalization with a benzene-1,3,5-tricarboxamide (BTA) derived supramolecular moiety. Such BTAs interact via directional, strong, yet reversible hydrogen-bonds with other identical BTAs. Herein, a protocol is presented that describes how to couple these BTAs to colloids and how to quantify the number of coupling sites, which determines the multivalency of the supramolecular colloids. Light scattering measurements show that the refractive index of the colloids is almost matched with that of the solvent, which strongly reduces the van der Waals forces between the colloids. Before photo-activation, the colloids remain well dispersed, as the BTAs are equipped with a photo-labile group that blocks the formation of hydrogen-bonds. Controlled deprotection with UV-light activates the short-range hydrogen-bonds between the BTAs, which triggers the colloidal self-assembly. The evolution from the dispersed state to the clustered state is monitored by confocal microscopy. These results are further quantified by image analysis with simple routines using ImageJ and Matlab. This merger of supramolecular chemistry and colloidal science offers a direct route towards light- and thermo-responsive colloidal assembly encoded in the surface-grafted monolayer.

A protocol for the synthesis and characterization of colloids coated with supramolecular moieties is described. These supramolecular colloids undergo self-assembly upon the activation of the hydrogen-bonds between the surface-anchored molecules by UV-light.

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical ...

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the development of antibody drug conjugates (ADCs) and nanomedicine, fluorescent microscopy and systems chemistry. For many of these applications, specificity of the bioconjugation method used is of prime concern. The Michael addition of maleimides with cysteine(s) on the target proteins is highly selective and proceeds rapidly under mild conditions, making it one of the most popular methods for protein bioconjugation.
We demonstrate here the modification of the only surface-accessible cysteine residue on yeast cytochrome c with a ruthenium(II) bisterpyridine maleimide. The protein bioconjugation is verified by gel electrophoresis and purified by aqueous-based fast protein liquid chromatography in 27% yield of isolated protein material. Structural characterization with MALDI-TOF MS and UV-Vis is then used to verify that the bioconjugation is successful. The protocol shown here is easily applicable to other cysteine - maleimide coupling of proteins to other proteins, dyes, drugs or polymers.

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

This protocol details the important steps required for the bioconjugation of a cysteine containing protein to a maleimide, including reagent purification, reaction conditions, bioconjugate purification and bioconjugate characterization.

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the ...

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single molecule level. An electrostatic self-assembly and covalent fixation (ESA-CF) process is used for the synthesis of the cyclic poly(tetrahydrofuran) (poly(THF)). The diffusive motion of individual cyclic polymer chains in a melt state is visualized using single molecule fluorescence imaging by incorporating a fluorophore unit in the cyclic chains. The diffusive motion of the chains is quantitatively characterized by means of a combination of mean-squared displacement (MSD) analysis and a cumulative distribution function (CDF) analysis. The cyclic polymer exhibits multiple-mode diffusion which is distinct from its linear counterpart. The results demonstrate that the diffusional heterogeneity of polymers that is often hidden behind ensemble averaging can be revealed by the efficient synthesis of the cyclic polymers using the ESA-CF process and the quantitative analysis of the diffusive motion at the single molecule level using the MSD and CDF analyses.

A protocol for the synthesis and characterization of diffusive motion of cyclic polymers at the single molecule level is presented.

단일 분자 수준에서 순환 고분자의 합성 및 용융 상태에서 그들의 확산 운동의 특성

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single ...

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. Detailed and generalized protocols are also presented for testing the catalytic activity of such complexes in arylation and Suzuki-Miyaura cross-coupling reactions. Representative results are shown for the catalytic activity of the four complexes in arylation and Suzuki-Miyaura type reactions. For each of the reactions investigated, at least one of the four complexes successfully catalyzed the reaction, qualifying them as promising candidates for catalysis of many carbon-carbon bond-forming reactions. The protocols presented are general enough to be adapted for the synthesis, purification and catalytic activity testing of new palladium N-heterocyclic carbene complexes.

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. The complexes were tested for catalytic activity in arylation and Suzuki-Miyaura reactions. For each reaction investigated, at least one of the four complexes successfully catalyzed the reaction.

보장<em&gt; N</em&gt; - 헤테로 사이 클릭 카벤 착물 : 벤즈 이미 다 졸리움 염으로부터의 합성 및 탄소 - 탄소 결합 형성 반응에서의 촉매 활성

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from ...

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분할 및 풀 합성 펩타이드 급 아미드 도서관의 특성

이핵 항암제로 플래티넘 비스 피리딘 계 리간드와 이들 착물의 합성 아미드 커플 링 반응

기능화의 합성 및 특성 금속 - 유기 프레임 워크

화이트 인의 활성화에 카르 보닐 장식 카르 벤의 제조 및 사용

아실 염화물과 칼륨 Alkynyltrifluoroborate 소금에서 Ynones의 금속이 합성

Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate

Synthesis and Characterization of Supramolecular Colloids

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

단일 분자 수준에서 순환 고분자의 합성 및 용융 상태에서 그들의 확산 운동의 특성

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