BURIED TREASURES: CASCADES WE HAVEN'T SEEN

Similar documents
A Stereoselective Synthesis of (+)-Gonyautoxin 3

Total Synthesis of Oxazolomycin A

Total Synthesis towards Maoecrystal V

Rhenium-Catalyzed Synthesis of Multisubstituted Aromatic Compounds via C-C Single-Bond Cleavage

Studies toward the Synthesis of Azadirachtin: Total Synthesis of a Fully Functionalized ABC Framework and Coupling with a Norbornene Domain

VI. Metal alkyls from oxidative addition / insertion

Additions to Metal-Alkene and -Alkyne Complexes

transmetallate displace ox. add. M + (insert) (β-elim.)

Electrophilic Carbenes

Highlights of Schmidt Reaction in the Last Ten Years

Domino Reactions in Total Synthesis! Reporter: Tianhe Yang! Supervisors: Prof. Yang! Prof. Chen! Prof. Tang!

Towards Maoecrystal V: A Comparison of Recent Strategies

o-palladated cat. [Chem. Comm (1999)] [Org. Lett. 2, 1826 (2000)] [Org. Lett. 2, 2881 (2000)] [JACS 41, 9550 (1999)]

O OH N. Me OMe N NH HO H Debenzoyltashironin NMe 2. Phalarine. Anne-Marie Dechert

Highlights in the Progress of Biomimetic Strategies for the Construction of Complex Natural Products. Chris Galliford 26 th August 2003

Synthesis of Resorcinylic Macrolides

Carbonyl Ylide Cycloadditions

Total Synthesis of the Proposed Structure of Briarellin J

11-Step Enantioselective Synthesis of ( )-Lomaiviticin Aglycon

Total Syntheses of Minfiensine

A Tandem Semipinacol Rearrangement/Alkylation of a-epoxy Alcohols: An Efficient and Stereoselective Approach to Multifunctional 1,3-Diols

Recent Development in. Tandem Radical Reactions (TRR)

Direct Oxidative Heck Cyclizations: Intramolecular Fujiwara-Moritani Arylations for the Synthesis of Functionalized Benzofurans and Dihydrobenzofurans

Chiral Diol Promoted Boronates Addi3on Reac3ons. Lu Yan Morken Group Boston College

Mild Cobalt-Catalyzed Hydrocyanation of Olefins with Tosyl Cyanide

Palladium-Catalyzed Oxygenation of Unactivated sp 3 C-H Bonds

Nine-Step Enantioselective Total Synthesis of (+)-Minfiensine

Total Syntheses of Nominine

A New Strategy for Efficient Synthesis of Medium and Large Ring Lactones without High Dilution or Slow Addition

Total Synthesis of Trioxacarcin DC-45-A2

Suggested solutions for Chapter 40

SECTION 12. «POT-POURRI» in Organic Synthesis (2018)

A Modular Approach to Polyketide Building Blocks: Cycloadditions of Nitrile Oxides and Homoallylic Alcohols

Total Synthesis of (+)-Sieboldine A J. Am. Chem. Soc. 2010, 132,

Asymmetric Radical Reactions. Zhen Liu 08/30/2018

Final Exam /340 ( CHEM 6352 Fall %) Name

CEM 852 Final Exam. May 6, 2010

Construction of Chiral Tetrahydro-β-Carbolines: Asymmetric Pictet Spengler Reaction of Indolyl Dihydropyridines

Total Synthesis of Cyclosporine: Access to N-Methylated Peptides via Isonitrile Coupling Reactions

Total Synthesis of the Chartellines

Literature Report. A 11-Steps Total Synthesis of Magellanine through a Gold(І)-Catalyzed Dehydro Diels-Alder Reaction

Literature Report IX. Cho, S. H. et al. Org. Lett. 2016, 18, Cho, S. H. et al. Angew. Chem. Int. Ed. 2017, 56,

Lecture 6: Transition-Metal Catalysed C-C Bond Formation

Mesoporous Organosilicas with Acidic Frameworks and Basic Sites in the Pores: An Approach to Cooperative Catalytic Reactions

Studies Toward the Total Synthesis of (±)-Noelaquinone

Asymmetric Catalysis by Lewis Acids and Amines

Synthesis of the Stenine Ring System from Pyrrole

Zr-Catalyzed Carbometallation

A Simple Introduction of the Mizoroki-Heck Reaction

Total Synthesis of (+/-)-Goniomitine via a Formal Nitrile/Donor-Acceptor Cyclopropane [3 + 2] Cyclization

Total Synthesis of ( )-Virginiamycin M2

JACS ASAP Article: Published 3/12/08. Lei Jiao, Changxia Yuan and Zhi-Xiang Yu. Current Literature: 3/29/08. David Arnold

Short Lit

Total Synthesis of Maoecrystal V: Early-Stage of C-H Functionalization and Lactone

Approaches to the Synthesis. of Tetrahydropyrans. (and closely related heterocycles)

Department of Chemistry, Colorado State University, Fort Collins, Colorado University of Colorado Cancer Center, Aurora, Colorado 80045

A synthesis of strychnine. by a longest linear sequence of six steps. Chem. Sci. 2011, 2, David B. C. Martin and Christopher D.

Lewis Base Activation of Lewis Acids: Development of a Lewis Base Catalyzed Selenolactonization

Catalytic synthesis of amines and amides

Syntheses of Leucascandrolide A. Supergroup Meeting August 4 th, 2004 Yu Yuan

Chiral Brønsted Acid Catalysis

Prof. Ang Li. Literature Seminar Kosuke Minagawa (D2)

Organocopper Chemistry

Spiro Monophosphite and Monophosphoramidite Ligand Kit

eatles Oasis - 199

Copper-Catalyzed Synthesis of Esters from Ketones. Alkyl Group as a Leaving Group.

Total Synthesis of ( )-Himandrine

Comparative Synthesis of Ingenol. Tyler W. Wilson SED Group Meeting

Metal Catalyzed Outer Sphere Alkylations of Unactivated Olefins and Alkynes

Concise, Asymmetric, Stereocontrolled Total Synthesis of Stephacidins A, B and Notoamide B

Synthesis of Azadirachtin: A Long but Successful Journey

Development of Chiral Phosphine Olefin Ligands and Their Use in Asymmetric Catalysis

Stereocontrolled organocatalytic synthesis of prostaglandin PGF 2 in seven steps

Heterocyclic Chemistry

Synthesis of Abyssomicin C. Marie-Caroline Cordonnier Litterature Review 23/01/2009

Studies on Heck and Suzuki Reactions Catalyzed by Palladium(0) and Wacker- Type Oxidative Cyclization Catalyzed by Palladium(II)

Ladderanes: Uses and Synthesis. Nicholas Anderson Denmark Group Meeting October 28, 2008

Intramolecular Huisgen-Type Cyclization of Platinum-Bound Pyrylium Ions with Alkenes and Subsequent Insertion into a Benzylic C-H Bond

Some questions and answers that we will get out of this example synthesis:

Asymmetric Nucleophilic Catalysis

A 1,3 Strain and the Anomeric Effect. Michael Shaghafi Chem. Topics Feb. 6, 2012

Organo-transition Metal Chemistry

Epoxidation with Peroxy Acids

Chiral Bronsted Acids as Catalysts

Enan$oselec$ve Total Synthesis of Amphidinolide F

Convergent Route to ent-kaurane Diterpenoids: Total Synthesis of Lungshengenin D and 1α6α- Diacetoxy-ent-kaura-9(11),16-dien- 12,15-dione

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

Use of Cp 2 TiCl in Synthesis

Ynolate Chemistry. Jeff Kallemeyn October 22, 2002

Organic Tutorials 3 rd Year Michaelmas Transition Metals in Organic Synthesis: (General paper level) ! 1! Reading

Massachusetts Institute of Technology Organic Chemistry 5.512

A Concise Synthesis of ( )- Aplyviolene Facilitated by a Stragetegic Ter<ary Radical Conjugate Addi<on

Chem 253 Problem Set 7 Due: Friday, December 3, 2004

Organocatalytic Umpolung via N- Heterocyclic Carbenes. Qinghe Liu Hu Group Meeting August 20 th 2015

STRATEGIES IN SYNTHESIS

!"#$%&&'!&(!)*+,-./!01"2.3$*4!"!#$!%$!%&'(') *+,!-$!%&'(').!'/ *&%&*,$.&-!"!3$!4$!5)01+!.*!06'2

Stable gold(iii) catalysts by oxidative addition of a carboncarbon

A Review of Total Synthesis of Spirotryprostatin A and B. Jinglong Chen Supergroup meeting Princeton University June

Total Synthesis of the Sesquiterpenoid Periconianone A Based on a Postulated Biogenesis

i-pr 2 Zn CHO N Sato, I.; Sugie, R.; Matsueda, Y.; Furumura, Y.; Soai, K. Angew. Chem., Int. Ed. Engl. 2004, 43, 4490

Transcription:

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: French, from Italian cascata, from cascare to fall, from (assumed) Vulgar Latin casicare, from Latin casus fall, Date: 1641 1: a steep usually small fall of water; especially :one of a series 2a : something arranged or occurring in a series or in a succession of stages so that each stage derives from or acts upon the product of the preceding <blood clotting involves a biochemical cascade > b: a fall of material (as lace) that hangs in a zigzag line 3: something falling or rushing forth in quantity <a cascade of sound> <a cascade of events> 4: ne-pot, sequential reactions involving more than one intermediate, preferrably 1) leading to an increase in molecular complexity and 2) without changing reaction conditions see: Chem. Commun., 2003, 551

Cascades Articulated Main Entry: 1cas cade Pronunciation: (")kas-'kad Function: noun Etymology: French, from Italian cascata, from cascare to fall, from (assumed) Vulgar Latin casicare, from Latin casus fall, Date: 1641 1: a steep usually small fall of water; especially :one of a series 2a : something arranged or occurring in a series or in a succession of stages so that each stage derives from or acts upon the product of the preceding <blood clotting involves a biochemical cascade > b: a fall of material (as lace) that hangs in a zigzag line 3: something falling or rushing forth in quantity <a cascade of sound> <a cascade of events> 4: ne-pot, sequential reactions involving more than one intermediate, preferrably 1) leading to an increase in molecular complexity and 2) without changing reaction conditions see: Chem. Commun., 2003, 551

Some Inspiration C 2 Me icolaou, K. C., J. Amer. Chem. Soc., 1982, 5555 1) 2, Pd/BaS 4 quinoline 2) toluene, 100 C 3 intermediates C 2 Me Me Me Me, TFA, 1,2-dichloroethane; Me Me Me K 2 C 3, 2, Me Johnson, W. S., J. Amer. Chem. Soc., 1971, 4330 2 intermediates Me 3 C P P R C 3 P Sorensen, E. J., J. Amer. Chem. Soc., 2002, 4552 Se mcpba, C 2 Cl 2 ; 40 C, CCl 3 4 intermediates P 1 3 C 3 C R P 1 P 2 C 3 C 3

Some Inspiration C 2 Me icolaou, K. C., J. Amer. Chem. Soc., 1982, 5555 1) 2, Pd/BaS 4 quinoline 2) toluene, 100 C 3 intermediates C 2 Me Me Me Me, TFA, 1,2-dichloroethane; Me Me Me K 2 C 3, 2, Me Johnson, W. S., J. Amer. Chem. Soc., 1971, 4330 2 intermediates Me 3 C P P R C 3 P Sorensen, E. J., J. Amer. Chem. Soc., 2002, 4552 Se mcpba, C 2 Cl 2 ; 40 C, CCl 3 4 intermediates P 1 3 C 3 C R P 1 P 2 C 3 C 3

Some Inspiration C 2 Me icolaou, K. C., J. Amer. Chem. Soc., 1982, 5555 1) 2, Pd/BaS 4 quinoline 2) toluene, 100 C 3 intermediates C 2 Me Me Me Me, TFA, 1,2-dichloroethane; Me Me Me K 2 C 3, 2, Me Johnson, W. S., J. Amer. Chem. Soc., 1971, 4330 2 intermediates Me 3 C P P R C 3 P Sorensen, E. J., J. Amer. Chem. Soc., 2002, 4552 Se mcpba, C 2 Cl 2 ; 40 C, CCl 3 4 intermediates P 1 3 C 3 C R P 1 P 2 C 3 C 3

Dihydropyridone Synthesis Chem. arm. Bull., 1987, 4730 Et, hu Et Me 2 C -C Me 2 C Me 2 C Me 2 C

Dihydropyridone Synthesis Chem. arm. Bull., 1987, 4730 Et, hu Et Me 2 C -C Me 2 C Me 2 C Me 2 C

Dihydropyridone Synthesis Chem. arm. Bull., 1987, 4730 Et, hu Et Me 2 C -C Me 2 C Me 2 C Me 2 C

Dihydropyridone Synthesis Chem. arm. Bull., 1987, 4730 Et, hu Et Me 2 C -C Me 2 C Me 2 C Me 2 C

Dihydropyridone Synthesis Chem. arm. Bull., 1987, 4730 Et, hu Et Me 2 C -C Me 2 C Me 2 C Me 2 C

Dihydropyridone Synthesis Chem. arm. Bull., 1987, 4730 Et, hu Et Me 2 C -C Me 2 C Me 2 C Me 2 C

Degredation to a Cyclohexadiene Angew. Chem. Int. Ed., 1975, 765. C 3 Li Et 2 C 3 Li

Degredation to a Cyclohexadiene Angew. Chem. Int. Ed., 1975, 765. C 3 Li Et 2 C 3 Li

Degredation to a Cyclohexadiene Angew. Chem. Int. Ed., 1975, 765. C 3 Li Et 2 C 3 Li

Degredation to a Cyclohexadiene Angew. Chem. Int. Ed., 1975, 765. C 3 Li Et 2 C 3 Li

Degredation to a Cyclohexadiene Angew. Chem. Int. Ed., 1975, 765. C 3 Li Et 2 C 3 Li

C 2 I 2, Zn/Cu Starting Material? Angew. Chem. Intern. Ed., 1975, 496 1. C 2 I 2, Zn/Cu 2. C 3 3. MeLi, Et 2 C 3, KtBu MeLi Li Et 2

C 2 I 2, Zn/Cu Starting Material? Angew. Chem. Intern. Ed., 1975, 496 1. C 2 I 2, Zn/Cu 2. C 3 3. MeLi, Et 2 C 3, KtBu MeLi Li Et 2

C 2 I 2, Zn/Cu Starting Material? Angew. Chem. Intern. Ed., 1975, 496 1. C 2 I 2, Zn/Cu 2. C 3 3. MeLi, Et 2 C 3, KtBu MeLi Li Et 2

C 2 I 2, Zn/Cu Starting Material? Angew. Chem. Intern. Ed., 1975, 496 1. C 2 I 2, Zn/Cu 2. C 3 3. MeLi, Et 2 C 3, KtBu MeLi Li Et 2

C 2 I 2, Zn/Cu Starting Material? Angew. Chem. Intern. Ed., 1975, 496 1. C 2 I 2, Zn/Cu 2. C 3 3. MeLi, Et 2 C 3, KtBu MeLi Li Et 2

Synthesis of a Tetrayne Tetrahedron Lett., 1976, 2663 Ac BuLi; CuCl BuLi Cu + Ac Li Cu + Ac Cu Symmetry Forbidden

Synthesis of a Tetrayne Tetrahedron Lett., 1976, 2663 Ac BuLi; CuCl BuLi Cu + Ac Li Cu + Ac Cu Symmetry Forbidden

Synthesis of a Tetrayne Tetrahedron Lett., 1976, 2663 Ac BuLi; CuCl BuLi Cu + Ac Li Cu + Ac Cu Symmetry Forbidden

Synthesis of a Tetrayne Tetrahedron Lett., 1976, 2663 Ac BuLi; CuCl BuLi Cu + Ac Li Cu + Ac Cu Symmetry Forbidden

Synthesis of a Tetrayne Tetrahedron Lett., 1976, 2663 Ac BuLi; CuCl BuLi Cu + Ac Li Cu + Ac Cu Symmetry Forbidden

Complex Polycycle J. Am. Chem. Soc., 2001, 12107 Bu 3 Sn SnBu 3 Pd(P 3 ) 4, D xidative Addition PdL n Migratory Insertion PdL n Transmetallation Bu 3 Sn SnBu 3 SnBu 3

Complex Polycycle J. Am. Chem. Soc., 2001, 12107 Bu 3 Sn SnBu 3 Pd(P 3 ) 4, D xidative Addition PdL n Migratory Insertion PdL n Transmetallation Bu 3 Sn SnBu 3 SnBu 3

Complex Polycycle J. Am. Chem. Soc., 2001, 12107 Bu 3 Sn SnBu 3 Pd(P 3 ) 4, D xidative Addition PdL n Migratory Insertion PdL n Transmetallation Bu 3 Sn SnBu 3 SnBu 3

Complex Polycycle J. Am. Chem. Soc., 2001, 12107 Bu 3 Sn SnBu 3 Pd(P 3 ) 4, D xidative Addition PdL n Migratory Insertion PdL n Transmetallation Bu 3 Sn SnBu 3 SnBu 3

Complex Polycycle Cont... J. Am. Chem. Soc., 2001, 12107 6 e- disrotatory - SnBu 3 SnBu 3 1 transfer -

Complex Polycycle Cont... J. Am. Chem. Soc., 2001, 12107 6 e- disrotatory - SnBu 3 SnBu 3 1 transfer -

A [3.2.0] Bicycle J. rg. Chem., 1994, 8092 Me 2 C TBDPS Si I TMSI, (TMS) 2 TBDPS I TMS C 2 Me TMS 2 TBDPS I - TMS C 2 Me TBDPS I Me TMS + TBDPS I C 2 Me TMS

A [3.2.0] Bicycle J. rg. Chem., 1994, 8092 Me 2 C TBDPS Si I TMSI, (TMS) 2 TBDPS I TMS C 2 Me TMS 2 TBDPS I - TMS C 2 Me TBDPS I Me TMS + TBDPS I C 2 Me TMS

A [3.2.0] Bicycle J. rg. Chem., 1994, 8092 Me 2 C TBDPS Si I TMSI, (TMS) 2 TBDPS I TMS C 2 Me TMS 2 TBDPS I - TMS C 2 Me TBDPS I Me TMS + TBDPS I C 2 Me TMS

A [3.2.0] Bicycle J. rg. Chem., 1994, 8092 Me 2 C TBDPS Si I TMSI, (TMS) 2 TBDPS I TMS C 2 Me TMS 2 TBDPS I - TMS C 2 Me TBDPS I Me TMS + TBDPS I C 2 Me TMS

A [3.2.0] Bicycle J. rg. Chem., 1994, 8092 Me 2 C TBDPS Si I TMSI, (TMS) 2 TBDPS I TMS C 2 Me TMS 2 TBDPS I - TMS C 2 Me TBDPS I Me TMS + TBDPS I C 2 Me TMS

A [3.2.0] Bicycle J. rg. Chem., 1994, 8092 Me 2 C TBDPS Si I TMSI, (TMS) 2 TBDPS I TMS C 2 Me TMS 2 TBDPS I - TMS C 2 Me TBDPS I Me TMS + TBDPS I C 2 Me TMS

A ydrindane Unpublished P 3, D P 3 P() 3

A ydrindane Unpublished P 3, D P 3 P() 3

A ydrindane Unpublished P 3, D P 3 P() 3

Another (the same) ydrindane oye, T., Unpublished Bn Grubbs Bn Bn Bn Bn Bn Bn

Another (the same) ydrindane oye, T., Unpublished Bn Grubbs Bn Bn Bn Bn Bn Bn

Another (the same) ydrindane oye, T., Unpublished Bn Grubbs Bn Bn Bn Bn Bn Bn

Summary Et, hu Et Me 2 C TBDPS TMSI (TMS) 2 I TBDPS TMS C 2 Me C 3 Li MeLi, Et 2 Et 2 Ac BuLi; CuCl P 3, D Bu 3 Sn SnBu 3 Bn Grubbs Bn Pd(P 3 ) 4, D