Studies toward the Synthesis of Azadirachtin: Total Synthesis of a Fully Functionalized ABC Framework and Coupling with a Norbornene Domain
|
|
|
- Rosaline Cunningham
- 5 years ago
- Views:
Transcription
1 Studies toward the Synthesis of Azadirachtin: Total Synthesis of a Fully Functionalized ABC Framework and Coupling with a Norbornene Domain Nicolaou and Co-workers Angew. Chem. Int. Ed. 2005, 44, 3443 C 2 Me Ac Me 2 C David Wipf Group 1 9/4/2005
2 Azadirachtin: Structural Mystery for 20 years -Isolated in 1968 from Azadirachta indica, the indian Neem tree, with no structure proposed. -Controversial structure proposed in 1975 by Nakanishi. Me 2 C Ac Me 2 C -In 1987, Kraus and Co-workers published the accepted structure Structure C 2 Me Ac Me 2 C Revised Structure -Azadirachtin is a potent insect anti-feedant, as well as growth inhibitor. -It is non-toxic, biodegradable, and "natural", and therefore an attractive pesticide. -Azadirachtin is unstable to mild acidic, basic and photolytic conditions. -Its biological mode of action is unknown. 16 contiguous chiral centers 7 tetrasubstitued carbons 7 rings Extremely dense oxygenation -Given is limited availability, simpler analogs are often targeted in hopes of maintaing effectiveness in the field. -Several groups have investigated its total synthesis. J. Chem. Soc. Chem. Commun. 1968, 23. J. Am. Chem. Soc. 1975, 97, Tetrahedron 1987, 43, 2779 David Wipf Group 2 9/4/2005
3 Some ther Approaches to Azadirachtin C 2 Me Shibasaki and Co-workers Ac Me 2 C 28 Steps TBDMS 3 steps from (-)-ethyl lactate R C 2 Me R TBDMS [] (-)-Azadirachtin R Me 2 C M Mori and Co-workers J. rg. Chem. 1989, 54, Steps TBS C 2 Me SePh Bu 3 Sn AIBN 28% TBS C 2 Me 12 Steps TBS Me Tetrahedron Lett. 1997, 38, 4429 Tetrahedron 1996, 52, David Wipf Group 3 9/4/2005
4 Ley and Co-workers Claisen-Radical Cyclization Approach C 2 Me Me 2 C C 2 Me Bn Me PMB MWI (15 x 1 min) o-dcb 180 C 88% Me 2 C C 2 Me Bn Me -All Lewis acid catalysis failed. PMB Ac Me 2 C 1) TESTf 2) DDQ 3) Na, CS 2, MeI TES Me 2 C C 2 Me Bn Me Bu 3 Sn AIBN 81% TES Me 2 C C 2 Me Bn Me S SMe TES Me 2 C C 2 Me Bn. Me TES Me 2 C C 2 Me Bn. Me rg. Lett. 2002, 4, 3847 Sterically Unprotonatable? David Wipf Group 4 9/4/2005
5 An Ireland-Claisen Approach C 2 Me Murai and Co-workers Ac Me 2 C C + Me DEIPS EDCI, DMAP 72% Me DEIPS Me DEIPS C 2 LMDS Me 2 SiCl 2 Toluene rg. Lett. 2002, 4, % dr: 4:1 -System lacks functionalization on decalin system. David Wipf Group 5 9/4/2005
6 Construction of the decalin system: Installation of dense oxygenation Ac Me 2 C C 2 Me 1) SEMCl (85%) 2) Li, N 3 (80%) SEM 1) NaB 4 (99%) 2) TBDPSCl (80%) 3) PPTs TBDPS SEM SEM 1) Comins' Reagent (72%, 2 stps) 2)Pd(Ac) 2, PPh 3 C, Me (89%) TBDPS C 2 Me 1) DIBAL (95%) 2)B 3, 2 2 (65%) SEM TBDPS ACIE, 2003, 42, ) Na, BnBr 2) TBAF (91%, 2 stps) 3) Swern (89%) SEM Bn Bn 1) KMDS, TESCl SEM Bn Bn 2) PhSeCl 3) % over three steps 1) LMDS, NCC 2 Me (93%) 2) Yb(Tf) 3, C 2 3) TBSTf (74%, 2 stps) 4) TBP, triton B (87%) SEM Me 2 C Bn TBS Bn David Wipf Group 6 9/4/2005
7 Final manipulation of the decalin system C 2 Me Ac Me 2 C SEM Bn Bn Me 2 C TBS 1) TBAF SEM Bn 1) (PhSe) 2, NaB 4 (91%) Bn 2) NaB 4 (63%) 2) Ac 2 (92%, 2 stps) Me 2 C 3) TBS 2, Pd/C (98%) 4) TESCl (82%) SEM TES Ac Ac Me 2 C Ac 1) DMP (91%) SEM Ac 1) NaCl 2 Ac 2) Ph 3 PC 2 (80%) 3) cat. DDQ (97%) 4) DMP (92%) Ac Me 2 C Ac 2) 0.5 M Cl (94%, 2 stps) 3) Se 2, TBP (51%) Ac Me 2 C Ac Decalin Partner David Wipf Group 7 9/4/2005
8 Temporary Linkage and Radical Cyclization C 2 Me Ac Ac Me 2 C Ac Me 2 C Ac + Me PMB Ac Ac Me 2 C Ac Br Br 2 80% Ac + PMB Ac Me 2 C ~1:1 Br Ac Me PMB + Me Br PMB xonium Intermediate TTMS, AIBN 80% TTMS, AIBN 80% Ac Ac Ac Me 2 C Ac Me Ac Ac Me 2 C Ac PMB Me Ac Me 2 C Ac. PMB Me Radical Cyclization Pathway 5-exo-trig cyclization followed by 1,5- shift and PMB loss 5-exo-trig cyclization followed by intermolecular quench -Cyclization extremely substrate dependant! David Wipf Group 8 9/4/2005
9 Towards Azadirachtin: xidative opening of the Acetal Linkage Ac Me 2 C C 2 Me Ac PMB 1) 2, Pd() 2 Ac Bz Ac Me 2 C Ac Me 2) BzCl Ac Me 2 C Ac Me TFA Ac Ac Me 2 C Ac Bz PCC 80% Ac Ac Me 2 C Ac Bz 75% over three steps David Wipf Group 9 9/4/2005
10 Conclusions C 2 Me Ac Me 2 C -A fully oxygenated decalin system was prepared and coupled to a model bicycle. -Radical cyclization and subsequent cleavage of the oxo-linkage provides high-yielding access to the sterically congested C8-C14 bond of Azadirachtin. -Bicycle lacks functionalization -Route to decalin partner is 32+ steps, often falling into protecting group traps, a consequence of the dense oxygenation. Ac Me Ac Me 2 C Ac PMB Decalin Partner Model Bicycle Ac PMB Ac Ac Me 2 C Ac Me Ac Me 2 C Ac Bz David Wipf Group 10 9/4/2005
Synthesis of Azadirachtin: A Long but Successful Journey
ynthesis of Azadirachtin: A Long but uccessful Journey Gemma E. Veitch, Edith Beckmann, Brenda J. Burke, Alistair Boyer, arah L. Maslen, and teven V. Ley Angew. Chem. Int. Ed. 2007, Early View And Gemma
SECTION 12. «POT-POURRI» in Organic Synthesis (2018)
SECTIN 12 «PT-PURRI» in rganic Synthesis (2018) 1 Total Synthesis of Erythromycin A via a Spiroketal ERYTRMYCIN A DESLNGCAMPS et al. Can. J. Chem. 1985, 63, 2810-2820. 2 Tetrahydropyran Derivative as Starting
Comparative Synthesis of Ingenol. Tyler W. Wilson SED Group Meeting
Comparative Synthesis of Ingenol Tyler W. Wilson SED Group eting 2.27.07 Ingenol: Biology, Isolation, and istory During WWII a latex was manufactured by precipitating the milky juice of the Euphorbia Ingen
Total Syntheses of Minfiensine
Total Syntheses of Minfiensine Douany, A. B.; umphreys, P. G.; verman, L. E.*; Wrobelski, A. D., J. Am. Chem. Soc. 2008, ASAP. D: 10.1021/ja800163v Shen, L.; Zhang, M.; Wu, Y.; Qin, Y.*, Angew. Chem. nt.
Studies Toward the Total Synthesis of (±)-Noelaquinone
Research Topic Seminar 18 June 2005 Studies Toward the Total Synthesis of (±)-Noelaquinone David Amantini WIPF GRUP The Role of Natural Products in Drug Discovery For thousands of years medicine and natural
The Story of Azadirachtin. Weiwu Ren
The Story of Azadirachtin Weiwu Ren 2015-12-17 Content 1 Introduction 2 Isolation and Structure Determination 3 Synthetic Study towards Azadirachtin 4 Total Synthesis of Azadirachtin Ley s Work Watanabe
Highlights in the Progress of Biomimetic Strategies for the Construction of Complex Natural Products. Chris Galliford 26 th August 2003
ighlights in the Progress of Biomimetic Strategies for the Construction of Complex Natural Products Chris Galliford 26 th August 2003 The Biomimetic Approach Inspiration for biomimetic synthesis of a target
Reporter: Yue Ji. Date: 2016/12/26
Literature Report (11) Total Synthesis of Rubriflordilactone B Reporter: Yue Ji Checker: Mu-Wang Chen Date: 2016/12/26 Yang, P.; Yao, M.; Li, J.; Li, Y.; Li, A.* Angew. Chem. Int. Ed. 2016, 55, 6964. Laboratory
Nine-Step Enantioselective Total Synthesis of (+)-Minfiensine
ine-step nantioselective Total Synthesis of (+)-Minfiensine Jones, S. B.; Simmons, B.; MacMillan, D. W. C.* J. Am. Chem. Soc. 2009, ASAP. DI: 10.1021/ja906472m Kara George Wipf Group - Current Literature
Towards Maoecrystal V: A Comparison of Recent Strategies
Towards Maoecrystal V: A Comparison of Recent Strategies Reactant/Reagent Current Literature: November 14, 2009 lissa Sprachman lissa Sprachman @ Wipf Group Page 1 of 14 12/28/2009 Maoecrystal V: Structural
Enan$oselec$ve Total Synthesis of Amphidinolide F
Enan$oselec$ve Total Synthesis of Amphidinolide F Subham Mahapatra and ich G. Carter regon State University Angew. Chem. nt. Ed., 2012, 51, 7948 Nicolas Millius Bern, 07.02.2013 ntroduc$on isolated from
11-Step Enantioselective Synthesis of ( )-Lomaiviticin Aglycon
11-Step Enantioselective Synthesis of ( )-Lomaiviticin Aglycon Seth B. erzon, Liang Lu, Christina M. Woo, and Shivajirao L. Gholap J. Am. Chem. Soc. ASAP DI 10.1021/ja200034b Melissa Sprachman Current
Total Synthesis of the Proposed Structure of Briarellin J
Total Synthesis of the Proposed Structure of Briarellin J Michael T. Crimmins, Mark C. Mans, and Abimael D. Rodríguez. rg. Lett. 2010, ASAP Ac Ac originally proposed structure revised structure Eric E.
Total Synthesis of (+)-Sieboldine A J. Am. Chem. Soc. 2010, 132,
Total Synthesis of (+)-Sieboldine A J. Am. Chem. Soc. 2010, 132, 7876 7877. Current Literature Presentation 10JUL2010 Michael Yang Mike Yang @ Wipf Group Page 1 of 15 7/10/2010 Sieboldine A Background
Facile preparation of α-amino ketones from oxidative ring-opening of aziridines by pyridine N-oxide
Facile preparation of α-amino ketones from oxidative ring-opening of aziridines by pyridine -oxide rg. Biomol. Chem., 2007, 5, 3428 Luo, Z.-B.; Wu, J.-Y.; ou, X.-L.; Dai, L.-X. Ts toluene Ts 80 o C John
Approaches to the Synthesis. of Tetrahydropyrans. (and closely related heterocycles)
Approaches to the Synthesis of Tetrahydropyrans (and closely related heterocycles) William Morris Literature Presentation July 6, 2004 I. Intro A Nomenclature B Prevalence in Nature C Biosynthetic Considerations
Radical Reactions. Radical Stability!!! bond dissociation energies X Y X + Y. bond BDE (kcal/mol) bond BDE (kcal/mol) CH 3 CH 3 CH 2 95 O H R 2 C H
adical eactions adical Stability!!! bond dissociation energies X Y X Y bond BDE (kcal/mol) bond BDE (kcal/mol) C 3 104 108 C 3 C 2 98 110 95 2 C 102 (-) 93 (C-) 92 C 3 C 3 36 89 85 C 3 C 3 80 adical eactions
Hirsutene and Δ 9(12) Capnellene. D. P. Curran (1986) Presenter: Mehdi Moemeni
irsutene and Δ 9(12) Capnellene D. P. Curran (1986) Presenter: Mehdi Moemeni Back Ground of Radical Structure In a modern context the first organic free radical identified was triphenylmethyl radical.
Total Syntheses of Nominine
Total Syntheses of ominine i Literature t Group eting Lizzie Bryan ctober 17, 2007 Aconite Alkaloids Atidane V eatchane Cycloveatchane Aconitane etisan Muratake,. M.; atsume, M.; akai,. Tetrahedron, 2006,
Syntheses of Leucascandrolide A. Supergroup Meeting August 4 th, 2004 Yu Yuan
Syntheses of Leucascandrolide A Supergroup Meeting August 4 th, 2004 Yu Yuan Leucascandrolide A Me Me Me Dambrosio, M.; Guerriero, A.; Debitus, C.; Pietra, F. elvetica Chimica Acta 1996, 79, 51-60 Me 1
Synthetic Developments Towards the Preparation of Erythromycin and Erythronolide Derivatives
ynthetic Developments Towards the Preparation of Erythromycin and Erythronolide Derivatives Russell C. mith Denmark Group Meeting 8-9-2005 most extensive project in organic synthesis this phenomenon is
Total Synthesis of Oxazolomycin A
Total Synthesis of xazolomycin A Me xazolomycin A Me Eto, K.; Yoshino, M.; Takahashi K.; Ishihara, J.; atakeyama S. rg. Lett. 2011, 13, 5398 Dimas Paz Wipf group- Current Literature ctober 8, 2011 Dimas
Total Synthesis of Maoecrystal V: Early-Stage of C-H Functionalization and Lactone
Literature Report Total Synthesis of Maoecrystal V: arly-stage of C- Functionalization and Lactone Assembly by Radical Cyclization Reporter: Ji Yue Checker: Chen Muwang Date: 2013/12/02 Zakarian, A. et
A Stereoselective Synthesis of (+)-Gonyautoxin 3
A Stereoselective Synthesis of (+)-Gonyautoxin 3 Mulcahy, J. V.; Du Bois, J. J. Am. Chem. Soc. 2008, 130, 12630-12631 Total Synthesis of (+)-Lithospermic Acid by Asymmetric Intramolecular Alkylation via
Convergent Route to ent-kaurane Diterpenoids: Total Synthesis of Lungshengenin D and 1α6α- Diacetoxy-ent-kaura-9(11),16-dien- 12,15-dione
Convergent Route to ent-kaurane Diterpenoids: Total Synthesis of Lungshengenin D and 1α6α- Diacetoxy-ent-kaura-9(11),16-dien- 12,15-dione Xiangbo Zhao, Wu Li, Junjie Wang, and Dawei Ma* Shanghai Institute
Total Synthesis towards Maoecrystal V
Total Synthesis towards Maoecrystal V isolated from the leaves of a Chinese medicinal herb, Isodon eriocalyx in 2004. structure was determined by comprehensive NMR and MS spectroscopic analysis and confirmed
Direct Oxidative Heck Cyclizations: Intramolecular Fujiwara-Moritani Arylations for the Synthesis of Functionalized Benzofurans and Dihydrobenzofurans
Direct xidative eck Cyclizations: Intramolecular Fujiwara-Moritani Arylations for the Synthesis of Functionalized Benzofurans and Dihydrobenzofurans by Zhang,.; Ferreira, E. M.; Stoltz, B. M. Angewandte
Massachusetts Institute of Technology Organic Chemistry 5.512
Massachusetts Institute of Technology rganic Chemistry 5.512 Problem Set 6 Solutions Stereocontrolled Carbonyl Reduction and Aldol Reactions May 5, 2006 Lucy Kohnen ( The target compound was used as an
Total Synthesis of (+/-)-Goniomitine via a Formal Nitrile/Donor-Acceptor Cyclopropane [3 + 2] Cyclization
![Total Synthesis of (+/-)-Goniomitine via a Formal Nitrile/Donor-Acceptor Cyclopropane [3 + 2] Cyclization](/thumbs/82/85235286.jpg "Total Synthesis of (+/-)-Goniomitine via a Formal Nitrile/Donor-Acceptor Cyclopropane [3 + 2] Cyclization")
Total Synthesis of (+/-)-Goniomitine via a Formal itrile/donor-acceptor Cyclopropane [3 + 2] Cyclization (-)-Goniomitine Christian L. Morales and Brian Pagenkopf* rganic Letters, ASAP Current Literature
A New Strategy for Efficient Synthesis of Medium and Large Ring Lactones without High Dilution or Slow Addition
A ew Strategy for Efficient Synthesis of Medium and Large ing Lactones without High Dilution or Slow Addition BF 3 Et 2 TIPS 2,4,6-collidine n + n+2 ' ' Zhao, W.; Li, Z; Sun, J. J. Am. Chem. Soc. 2013
Total Synthesis of (-)-Mersicarpine
Total Synthesis of (-)-Mersicarpine Rie akajima, Tsuyoshi gino, Satoshi Yokoshima, and Tohru Fukuyama. J. Am. Chem. Soc. ASAP Published online 1-7-2010 Eric E. Buck Current Literature January 23, 2010
Bioinspired Total Synthesis of Agelastatin A
Bioinspired Total Synthesis of Agelastatin A Jeremy Chris P. Reyes and Daniel Romo Benjamin R. Eyer Wipf Group-Current Literature August 25, 2012 Angewandte Chemie International Edition. 2012, 51(28),
Stemona Alkaloids. tuberostemonol. OMe O O. neostemonine. OMe O O. protostemonine
I. Introduction 9 9a 8 1 2 The Stemonaceae plant family, which comprises over 0 species, produces a large class of structurally diverse alkaloids featuring a conserved pyrrolo [1,2-a] azepine = perhydroazaazulene
I. Introduction. II. Retrosynthetic Analysis. Andrew Baggett. Liu lab
Total Synthesis of Limonin Shuji Yamashita,* Akito Naruko, Yuki Nakazawa, Le Zhao, Yujiro Hayashi, Masahiro Hirama Tohoku University, Department of Chemistry, Aramaki-aza aoba, Aoba-ku, Sendai 980-8578
Prof. Ang Li. Literature Seminar Kosuke Minagawa (D2)
Prof. Ang Li Literature Seminar 2017. 10. 28 Kosuke Minagawa (D2) 1 2 3 aspidodasycarpine 1) 2 C sespenine 3) atural Products Synthesized by Ang Li group clostrubin 6) drimentine A 7) i-bu rubriflordilactone
Synthesis of Amphidinolide X and an Exploration of Key Reactions
PJM 1/12/05 Synthesis of Amphidinolide X and an Exploration of Key eactions Lepage,.; Kattnig, E.; Furstner, A. JACS, 2004, 126, 15970-15971. 7 13 1 6 19 - Produced by marine dinoflagellates, Amphidinium
Asymmetric Copper-Catalyzed Synthesis of α-amino Boronate Esters from N-tert- Butanesulfinyl Aldimines
Asymmetric Copper-Catalyzed Synthesis of α-amino Boronate Esters from -tert- Butanesulfinyl Aldimines R BR 2 J. Am. Chem. Soc. 2008, 130, 6910. Melissa A. Beenen, Chihul An, and Jonathan A. Ellman rrent
Synthesis of the Phomoidrides (CP 225,917 & CP 263,114) Chem. Rev. 2003, 103, 2691.
ynthesis of the Phomoidrides (P 225,917 & P 263,114) hem. Rev. 2003, 103, 2691. 15 7 26 2 7 16 14 1 2 5 7 2 7 1 2 1 4 2 6 1 5 9 1 7 1 9 2 9 1 5 (+)-P hom oidr ide A ; 7 = (P- 225,917) (+)-P hom oidr ide
James D. White. A very productive professor 64 students graduated from his lab 94 postdocs have worked in his lab. Education Experience
A very productive professor 64 students graduated from his lab 94 postdocs have worked in his lab Education Experience Fraser Fleming University of Drexel Pavel agory University of Michigan Cambridge University,
Approaches to the Synthesis of Macquarimicins and Cochleamycins
Ac Macquarimicin A Cochleamycin A Approaches to the Synthesis of Macquarimicins and Cochleamycins Drew Adams Friday Seminar March 18, 2005 Isolation and Activity Ac Isolated in 1995 from Micromonospora
JOC: 1985 Year in Review
Baran Group eting JC: 1985 Year in eview Syntheses discussed: thodoligies discussed: Quadrone 2 C (+)-irsutic Acid C (±) Coriolin (!)-Longifolene (!)-astanecine Manganese (III)-mediated "-lactone annulation
Literature Report. A 11-Steps Total Synthesis of Magellanine through a Gold(І)-Catalyzed Dehydro Diels-Alder Reaction
Literature Report 11-Steps Total Synthesis of Magellanine through a Gold(І)-Catalyzed ehydro iels-lder Reaction Reporter: ong-qiang Shen Checker: Cong Liu ate: 2017/06/19 McGee, P.; Bétournay, G.; Barabé,
Hennoxazole A. Philip Williams Group Meeting December 12, OMe. OMe 1 6 O H
ennoxazole A 1 6 11 17 24 Philip Williams Group eting December 12, 2007 Discovered Discovered by Paul cheuer at the University of awaii in 1991. Isolated 480mg ennoxazole A from 4.5kg from the sponge Polyfibrospongia
Total Synthesis of Peloruside A Through Kinetic Lactonization and Relay Ring-Closing Metathesis Cyclization Reactions
Total Synthesis of Peloruside A Through Kinetic Lactonization and Relay Ring-Closing Metathesis Cyclization Reactions Thomas R. oye, Junha Jeon, Lucas C. Kopel, Troy D. Ryba, Manomi A. Tennakoon, and Yini
Electrophilic Carbenes
Electrophilic Carbenes The reaction of so-called stabilized diazo compounds with late transition metals produces a metal carbene intermediate that is electrophilic. The most common catalysts are Cu(I)
An Analysis of the Total Syntheses of Aphidicolin
An Analysis of the Total Syntheses of Aphidicolin An Evans Group Afternoon Seminar Krista Beaver March 20, 1998 A B D C Aphidicolin Isolated from the fungus Cephalosporium aphidicola (esp, Chem. Comm.1972,
Progress toward the Total Synthesis of Pleurotin
Progress toward the Total Synthesis of Pleurotin SINYA IIMURA Wipf Research Group Meeting July 9th, 2005 Shinya Iimura @ Wipf Group 1 7/10/2005 Presentation utline! Isolation and Structure! Biological
Total Synthesis of ( )-Himandrine
Total Synthesis of ( )-imandrine M. Movassaghi,* M. Tjandra and J. Qi J. Am. hem. Soc. 2009, 131, 9648-9650 Bz Adam T. oye urrent Literature ctober 3, 2009 Adam oye @ Wipf Group Page 1 of 22 10/3/2009
Short Literature Presentation 10/4/2010 Erika A. Crane
Copper-Catalyzed Enantioselective Synthesis of trans-1- Alkyl-2-substituted Cyclopropanes via Tandem Conjugate Additions-Intramolecular Enolate Trapping artog, T. D.; Rudolph, A.; Macia B.; Minnaard, A.
Huang, C.; Gevorgyan, V. J. Am. Chem. Soc. 2009, 131, Daniel Tzvi Cohen Short Literature Feb. 23, MeO HO OH. COOH ( )-Plicatic Acid OH OH
Asymmetric Total Synthesis of ( )-Plicatic Acid via a Highly Enantioselective and Diastereoselective Nucleophilic Epoxidation of Acyclic Trisubstituted lefins H H H H CH ( )-Plicatic Acid H H Sun, B.F.;
Large-Scale Synthesis of the Anti-Cancer Marine Natural Product (+)-Discodermolide
61.7 g prepared in 39 steps 43 chemists worked on the project which lasted 20 months Chris Kendall @ Wipf Group 1 3/27/04 8 22 1 5 24 carbon linear polypropionate chain containing stereocenters (6 hydroxyl
Palladium-Catalyzed Oxygenation of Unactivated sp 3 C-H Bonds
Palladium-Catalyzed xygenation of Unactivated sp 3 C- Bonds Pd(Ac) 2 5 mol% PhI(Ac) 2 1.1 eq. Pd 2 Ac Desai, L. P.; ull, K. L.; Sanford *, M. S. University of Michigan J. Am. Chem. Soc. 2004, 126, ASAP
Strategies for Stereocontrolled Synthesis
Chemistry. Synthetic rganic Chemistry II Lecture 3 March, 2007 Rick L. Danheiser Massachusetts Institute of Technology! Thermodynamic Control Strategies! Kinetic Control Strategies! Strategies for the
A Unified Strategy to ent-kauranoid Natural Products: Total Syntheses of ( )-Trichorabdal A and ( )-Longikaurin E
A Unified Strategy to ent-kauranoid Natural Products: Total Syntheses of ( )-Trichorabdal A and ( )-Longikaurin E John T. S. Yeoman, Victor W. Mak, and Sarah E. Reisman. J. Am. Chem. Soc. 2013, 135, 11764.
Total Synthesis of Gracilioether F: Development and Application of Lewis Acid Promoted Ketene-Alkene [2+2] Cycloadditions and Late Stage C-H Oxidation
![Total Synthesis of Gracilioether F: Development and Application of Lewis Acid Promoted Ketene-Alkene [2+2] Cycloadditions and Late Stage C-H Oxidation](/thumbs/94/118539468.jpg "Total Synthesis of Gracilioether F: Development and Application of Lewis Acid Promoted Ketene-Alkene [2+2] Cycloadditions and Late Stage C-H Oxidation")
Total Synthesis of Gracilioether F: Development and Application of Lewis Acid Promoted Ketene-Alkene [2+2] ycloadditions and Late Stage - xidation hristopher M. Rasik and M. Kevin Brown Angew. hem. Intd.
Total synthesis of marine natural products without using protecting groups
Total synthesis of marine natural products without using protecting groups ature (London, United Kingdom), Vol 446, March 2007, p. 404-408 Phil S. Baran, Thomas J. Maimone & Jeremy M. Richter Presented
Protecting Groups in Organic Synthesis-1 Ready
Protecting Groups in rganic Synthesis-1 eady Protecting Groups for Alcohols Protecting groups are a sad fact of synthetic chemistry They are usually needed, but rarely desired Many syntheses have stalled
JACS ASAP Article: Published 3/12/08. Lei Jiao, Changxia Yuan and Zhi-Xiang Yu. Current Literature: 3/29/08. David Arnold
Tandem h(i)-catalyzed [(5+2)+1] Cycloaddition/Aldol eaction for the Construction of Linear Triquinane Skeleton: Total Syntheses of (+)-irsutene and (+)-1- Desoxyhypnophilin JACS ASAP Article: Published
a-aminoallylation of Aldehydes with Ammonia: Stereoselective Synthesis of Homoallylic Primary Amines
a-aminoallylation of Aldehydes with Ammonia: Stereoselective Synthesis of omoallylic Primary Amines 1 3 2 3 ML n 1 2 2 3 Masaharu Sugiura, Keiichi irano and Shu Kobayashi JACS ASAP ryan Wakefield @ Wipf
Asymmetric Catalysis by Lewis Acids and Amines
Asymmetric Catalysis by Lewis Acids and Amines Asymmetric Lewis acid catalysis - Chiral (bisooxazoline) copper (II) complexes - Monodentate Lewis acids: the formyl -bond Amine catalysed reactions Asymmetric
A Concise Synthesis of ( )- Aplyviolene Facilitated by a Stragetegic Ter<ary Radical Conjugate Addi<on
A Concise Synthesis of ( )- Aplyviolene Facilitated by a Stragetegic Ter
Total Synthesis of the Sesquiterpenoid Periconianone A Based on a Postulated Biogenesis
Total Synthesis of the Sesquiterpenoid Periconianone A Based on a Postulated Biogenesis C 3 C3 Liffert, R., Linden, A., Gademann, K. J. Am. Chem. Soc. 2017, 139, 16096 Presented by: Brendyn Smith CEM 852
Total Synthesis of ( )-Virginiamycin M2
Total Synthesis of ( )-Virginiamycin M2 Jie Wu and James S. Panek, Angewandte Chemie International Edition, 2010, 49, 6165-6168 btained from the CDC Public ealth Image Library. Image credit: CDC/Dr. David
O OH N. Me OMe N NH HO H Debenzoyltashironin NMe 2. Phalarine. Anne-Marie Dechert
Recent ighlights ht from the Danishefsky Laboratory 11-0-Debenzoyltashironin 2 Phalarine Anne-Marie Dechert ovember 7, 2007 11-0-Debenzoyltashironin Background and Structural Features Isolated from the
Reductive Elimination from High-Valent Palladium. Kazunori Nagao MacMillan Group Meeting
Reductive Elimination from igh-valent Palladium Kazunori agao MacMillan Group eting Why do people focus on rging with C activation Facile reductive elimination DG C palladacycle oxidant complex C etero
Ladderanes: Uses and Synthesis. Nicholas Anderson Denmark Group Meeting October 28, 2008
Ladderanes: Uses and Synthesis icholas Anderson Denmark Group Meeting ctober 28, 2008 utline Ladderane types and classifications Potential applications of ladderanes Synthesis of ladderanes Ladderane natural
BURIED TREASURES: CASCADES WE HAVEN'T SEEN
BURIED TREASURES: CASCADES WE AVE'T SEE Me Me Me 2 3 C C 3 3 C C 3 C 2 Me R. Robinson, J. Chem. Soc., 1917, 762 Cascades Articulated Main Entry: 1cas cade Pronunciation: (")kas-'kad Function: noun Etymology:
Chapter 5 Three and Four-Membered Ring Systems
Chapter 5 Three and Four-mbered ing ystems 5.1 Aziridines Aziridines are good alkylating agents because of their tendency to undergo ring-opening reaction with nucleophiles 例 mitomycin C antibiotic and
[3,3]-sigmatropic Processes. [2,3]-sigmatropic Processes. Ene Reactions. Generalized Sigmatropic Processes X,Y=C, N, O, S X,Y=C, N, O, S
![[3,3]-sigmatropic Processes. [2,3]-sigmatropic Processes. Ene Reactions. Generalized Sigmatropic Processes X,Y=C, N, O, S X,Y=C, N, O, S](/thumbs/94/119475672.jpg "[3,3]-sigmatropic Processes. [2,3]-sigmatropic Processes. Ene Reactions. Generalized Sigmatropic Processes X,Y=C, N, O, S X,Y=C, N, O, S")
Generalized igmatropic Processes [3,3]-sigmatropic Processes 1 3,=C,,, 1 3 3,=C,,, 3 [2,3]-sigmatropic Processes 1 3,=C,,, 1 3 Ene eactions 1 3 1 3 Cope earrangement [3,3]- igmatropic earrangements Transition
Enantioselective Synthesis of (+)-Cephalostatin 1
1 Cephalostatin 1 Enantioselective Synthesis of (+)-Cephalostatin 1 Tingting Mo Wipf Group Current Lit. Dec. 26 2009 Tingting Mo @ Wipf Group Page 1 of 9 /28/2009 2 Background 1972, marine worm Cephalodiscus
Total Synthesis of Palau amine
Total Synthesis of Palau amine Seiple, I. B.; Su, S.; Young, I. S.; Lewis, C. A.; Yamaguchi, J.; Baran, P. S. Angew. Chem. Int. Ed. 2009, early view. 2 2 2 2 2 2 Chad opkins Wipf Group Literature Presentation
CEM 852 Final Exam. May 6, 2010
CEM 852 Final Exam May 6, 2010 This exam consists of 7 pages. Please make certain that your exam has all of the necessary pages. Total points possible for this exam are 150. n answering your questions,
VI. Metal alkyls from oxidative addition / insertion
V. Metal alkyls from oxidative addition / insertion A. Carbonylation - C insertion very facile, metal acyls easily cleaved, all substrates which undergo oxidative addition can in principle be carbonylated.
Total Synthesis of the Chartellines
Total Synthesis of the Chartellines X Y chartelline A, X = Y = chartelline B, X =, Y = chartelline C, X = Y = Mariam Shamszad ovember 1, 2006 Background Chartellines A, B, and C were isolated in the 1980s
Additions to Metal-Alkene and -Alkyne Complexes
Additions to tal-alkene and -Alkyne Complexes ecal that alkenes, alkynes and other π-systems can be excellent ligands for transition metals. As a consequence of this binding, the nature of the π-system
C-O C-O C-N A A. (KHMDS) C-N (scheme 1) C-O C-N (1)
C- C- C- A A 2007 2008 -t- (Boc)-- (MM)- () (KMDS) C- (scheme ) C- C- () C- C- C- C- C- C- B C- B (scheme 2) C- B (2) C- manzacidin A Manzacidine A (5) - ATP (fig. ) C- 5 Ph MM Boc ethyl lactate X n=,2
Synthesis of Abyssomicin C. Marie-Caroline Cordonnier Litterature Review 23/01/2009
Synthesis of Abyssomicin C Marie-Caroline Cordonnier Litterature Review 23/01/2009 Isolation Isolated in 2004 from the actinomycete Verrucosispora strain collected from a sediment at a depth of 289m in
The Vetivane Sesquiterpenes
Group eting In 1940, Pfau and Plattner proposed structures for b-vetivone, one of the constituents of vetiver oil, an aromatic oil from vetiver grass. The structure was assigned based on extensive degradative
Enantioselective Synthesis of Pactamycin, a Complex Antitumor Antibiotic
Journal Club (3) Tomoya akamura Enantioselective Synthesis of Pactamycin, a Complex Antitumor Antibiotic Justin T. Malinowski, Robert J. Sharpe, Jeffrey S. Johnson Science 03, 30, 80 8.. Introduction -.
Intramolecular Huisgen-Type Cyclization of Platinum-Bound Pyrylium Ions with Alkenes and Subsequent Insertion into a Benzylic C-H Bond
Intramolecular uisgen-type Cyclization of Platinum-Bound Pyrylium Ions with Alkenes and Subsequent Insertion into a Benzylic C- Bond Chang o h,* Ji o Lee, Su Jin Lee, Jae Il Kim, and Chang Seop ong Department
Short Lit
Short Lit. - 7-12-2010 Jonathan A. Brekan a Department of Chemistry, orthwestern University, 2145 Sheridan Road, 60208, Evanston, Illinois, United States of America Citronellal Monoterpenoid distillate
A Highly Convergent and Biomimetic Total Synthesis of Portentol
A ighly Convergent and Biomimetic Total Synthesis of Portentol portentol B. Cheng, D. Trauner, J. Am. Chem. Soc. 2015, 137, 13800 13083 Departement of Chemistry and Center for Integrated Protein Science
Organocatalytic stereoselective [8+2] and [6+4] cycloadditions
![Organocatalytic stereoselective [8+2] and [6+4] cycloadditions](/thumbs/85/92727022.jpg "Organocatalytic stereoselective [8+2] and [6+4] cycloadditions")
rganocatalytic stereoselective [8+2] and [6+4] cycloadditions Joel Walker Current Literature March 4 th, 2017 Mose, R.; Preegel, G.; Larsen, J.; Jakobsen, S.; Iversen, E..; Jørgensen, K. A. Nature Chem.
Direct Organocatalytic Enantioselective Mannich Reactions of Ketimines: An Approach to Optically Active Quaternary α-amino Acid Derivatives
Direct rganocatalytic Enantioselective Mannich eactions of Ketimines: An Approach to ptically Active Quaternary α-amino Acid Derivatives Wei Zhang, Steen Saaby, and Karl Anker Jorgensen The Danish ational
Lewis Base Activation of Lewis Acids: Development of a Lewis Base Catalyzed Selenolactonization
Lewis Base Activation of Lewis Acids: Development of a Lewis Base Catalyzed Selenolactonization Denmark, S.E. and Collins, W.R. rg. Lett. 2007, 9, 3801-3804. C 2 H + Se Lewis Base CH 2 Cl 2 Se Presented
Nickel-Catalyzed Three-Component [3+2+2] Cocyclization of Ethyl Cyclopropylideneacetate and Alkynes
![Nickel-Catalyzed Three-Component [3+2+2] Cocyclization of Ethyl Cyclopropylideneacetate and Alkynes](/thumbs/77/74720708.jpg "Nickel-Catalyzed Three-Component [3+2+2] Cocyclization of Ethyl Cyclopropylideneacetate and Alkynes")
Nickel-Catalyzed Three-Component [3+2+2] Cocyclization of Ethyl Cyclopropylideneacetate and Alkynes Selective Synthesis of Multisubstituted Cycloheptadienes 1 2 Cat. Ni 0 1 2 Komagawa, S.; Saito, S. Angew.
Operating mechanisms: Useful articles:
Useful articles: Fairlamb, ACIEE, 2004, 1048. Aubert et al., Chem. Rev., 2002, 813. Fletcher et al., J. Chem. Soc., Perkin 1, 2000, 1657. Fürstner et al., Chem. Eur. J., 2004, 4556. Kozmin et al. Adv.
Scalable Total Syntheses of N-Linked Tryptamine Dimers by Direct Indole-Aniline Coupling: Psychotrimine and Kapakahines B and F
Scalable Total Syntheses of -Linked Tryptamine Dimers by Direct ndole-aniline Coupling: Psychotrimine and Kapakahines B and F tryptamine X electrophilic nitrogen source 2 methodology development innovative
Domino Reactions in Total Synthesis! Reporter: Tianhe Yang! Supervisors: Prof. Yang! Prof. Chen! Prof. Tang!
1! Domino Reactions in Total Synthesis! Reporter: Tianhe Yang! Supervisors: Prof. Yang! Prof. Chen! Prof. Tang! 2! utline! 1. Brief Introduction! 2. ucleophilic Dominoes! 3. Electrophilc Dominoes! 4. Radical
Concise, Asymmetric, Stereocontrolled Total Synthesis of Stephacidins A, B and Notoamide B
Concise, Asymmetric, Stereocontrolled Total Synthesis of Stephacidins A, B and otoamide B (+)-avrainvillamine (+)-notoamide B 20 51 21 55 (-)-stephacidin B In 2002, Bristol-Myers Squibb reported the biologically
Synthesis of the Stenine Ring System from Pyrrole
Current Literature Presentation gor psenica 06/18/2011 Synthesis of the Stenine Ring System from Pyrrole Bates, R. W.; Sridhar, S. J. rg. Chem., 2011, 76, 5026 5035 gor psenica @ Wipf Group Page 1 of 16
Keisuke Suzuki. Baran lab Group Meeting 6/11/16. Shigenobu Umemiya. Akira Suzuki. Takanori Suzuki (Hokkaido University)
197.D., Teruaki Mukaiyama, University of Tokyo 193 Assistant Professor, Keio University 197 Lecturer, Keio University 199 Assocate Professor, Keio University 1990 Visiting Professor, ET 1994 ull Professor,
Sonogashira Couplings of Aryl Bromides: Room Temperature, Water Only, No Copper
Sonogashira Couplings of Aryl omides: Room Temperature, Water nly, o Copper uce. Lipshutz, David W. Chung, and ian Rich rg.lett. ASAP Article Presentation By ora Jameson Current Lit 08/30/2008 ora Jameson
Application of Two Direct C(sp 3 )-H Functionalizations for the Total Synthesis of (+)-Lactacystin
Application of Two Direct C(sp 3 )- Functionalizations for the Total Synthesis of (+)-Lactacystin two stereoselective C(sp 3 )- functionalisations 2 C S Ac (S)-pyroglutaminol (+)-lactacystin S. Yoshioka,
Cladiellin, Briarellin, Asbestinin & Sarcodictyin Diterpenes
Cladiellin, Briarellin, Asbestinin & Sarcodictyin Diterpenes I. Introduction Cembranes are a large class of macrocyclic diterpenes (C 20) isolated from a diverse group of organisms (both plants and animals)
A Modular Approach to Polyketide Building Blocks: Cycloadditions of Nitrile Oxides and Homoallylic Alcohols
A Modular Approach to Polyketide Building Blocks: Cycloadditions of itrile xides and Homoallylic Alcohols rganic Letters, 2005, ASAP ina Lohse-Fraefel and Erick M. Carreira * H H H + ' 1. t-bucl, -78 C
Concise Total Synthesis of Variocolortides A and B through an Unusual Hetero-Diels- Alder Reaction!
Concise Total Synthesis of Variocolortides A and B through an Unusual etero-diels- Alder Reaction! Christian A. Kuttruff, endrik Zipse, and Dirk Trauner! ACIE Early View, DI: 10.1002/anie.201006154! Marija
Highly selective synthetic organic reactions utilizing cleavage of C-Cl bond
Highly selective synthetic organic reactions utilizing cleavage of C- bond SmI 2 Reformatsky rg. Lett. 2008, 10, 5453.) C- C-C C- C-C C- C-- C- Chem. Lett. 2009, 38, 1078. Sc(Tf) 3 (Chem. Lett. 2010, 39,
Back to Sugars: Enzymatic Synthesis
Back to Sugars: Enzymatic Synthesis Zhensheng Ding ov. 04 orthrup, A. B.; M acm illan, D. W. C. Science 2004, 305, 1752 orthrup, A. B. and MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124, 6798-6799 orthrup,
Introduction to Synthesis: Design (CHE686) Spring 2015 Exam #1 3/6/15
Introduction to ynthesis: Design (CE686) pring 2015 Exam #1 3/6/15 AME: KEY ome Pointers: 1. ELAX!! 2. ead the instructions for each question carefully. Be sure you understand what is required. If you