A Route to Carbasugar Analogues - Jonathan Clayden - The ...

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Acknowledgments I would like to thank Jonathan for his guidance, support, barbeques and boat trips over the last three-and-a-bit years. I am also very grateful to Andy Payne who supervised me during my period of work at GSK Harlow, and to Bob and Phyllis who made my stay there much more enjoyable than it would otherwise have been. I am of course thankful to the technical staff at the University of Manchester, especially Val, Gareth and Rohana; and to Phil and John at GSK. Madeleine and Jim have always been very helpful when I’ve been stuck squinting at the crystal structures they always seem able to solve. Johanna and Eric also deserve a special mention for their assistance with everything EPR, and for their willingness to let me taint their machines with organic compounds. I have enjoyed spending the past years with members of the Clayden group both inside and outside of lab. Particular thanks to Betson, Wes, and Tim for proof reading and generally being great friends and lab-neighbours. I am also incredibly grateful to Nuria, Beckii, Olga and James for the conversations, and over the past months for allowing me to experiment vicariously. Cousin It for being generally great, Heloise for being a wonderful hostess, Lluis for general mischief in Japan, Worral for his company through the night-time hours (both lab and pub), Vas for being Vas, and Simon for his enthusiastic morning greetings and Glasto. I am been grateful to everyone else for contributing to a friendly atmosphere, in particular Abby, Riz, Tom, Damo, Steve, James, Jordi, Boris, Pickworth, and Uli Uli Uli Uli. I have been very fortunate to have had a string of insightful mentors over the years; to them I am indebted for the care and time they have taken in educating me and my peers. I am grateful to my parents for always supporting me in everything I do, and being there to offer advice or support whenever I need it. Special thanks of course go to Giudi, for far too many reasons to list. Her support, tolerance and love over the last three years have helped me to get through the lows and embrace the highs. – LLFF 9
Abbreviations & Conventions Ac acetate AD Sharpless asymmetric dihydroxylation Anh. Anhydrous AIBN azobisisobutyronitrile Ar aryl aq aqueous BHA butylated hydroxyanisole / 2,6-di-tert-butyl-4-methoxyphenol Bn benzyl Bu butyl t-Bu tert-butyl n-Bu n-butyl s-Bu sec-butyl Bz benzoyl c. circa cat. catalytic CDI 1,1’-carbonyldiimidazole c-Hex cyclohexyl CI chemical ionisation mass spectroscopy CIP contact ion pair CIPE complex-inducted proximity effect conv. conversion of starting material COSY 1 H- 1 H correlation spectroscopy Δ heat under reflux DCE dichloroethane DEPT distortionless enhancement by polarisation transfer DIC N,N'-Diisopropylcarbodiimide DIAD diisopropyl azodicarboxylate DMAP N,N-dimethyl-4-aminopyridine DMF N,N-dimethylformamide DMPU dimethylpropyleneurea / dimethylhexahydro-2-pyrimidinone d.r. diastereomeric ratio 10
Page 1 and 2: Dearomatising Addition of Organolit
Page 3 and 4: 2.3 Synthetic Scope 64 2.3.1 Organo
Page 5 and 6: Abstract Dearomatising Addition of
Page 7: The Author The Author graduated fro
Page 11 and 12: RDS rate determining step R f RC rt
Page 14 and 15: Chapter 1: Introduction Chapter 1 -
Page 16 and 17: Chapter 1: Introduction controlled
Page 18 and 19: Chapter 1: Introduction diastereome
Page 20 and 21: Chapter 1: Introduction combine mor
Page 22 and 23: Chapter 1: Introduction O Ar Cl TMP
Page 24 and 25: Chapter 1: Introduction conditions,
Page 26 and 27: Chapter 1: Introduction chiral oxaz
Page 28 and 29: Chapter 1: Introduction Again a lar
Page 30 and 31: Chapter 1: Introduction 34 Scheme 1
Page 32 and 33: Chapter 1: Introduction The amino a
Page 34 and 35: Chapter 1: Introduction It was envi
Page 36 and 37: Chapter 1: Introduction COR' i) ATP
Page 38 and 39: Chapter 1: Introduction O i) ATPH,
Page 40 and 41: Chapter 1: Introduction 1.4 Nucleop
Page 42 and 43: Chapter 1: Introduction Unlike the
Page 44 and 45: Chapter 1: Introduction Diene (-)-8
Page 46 and 47: Chapter 1: Introduction A scheme su
Page 48 and 49: Chapter 1: Introduction Cl R + 93 S
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Chapter 2 - Dearomatising additions
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3.1 - Oxazoline synthesis 3.1.1.a H
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3.1 - Oxazoline synthesis O Ar OH i
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3.1 - Oxazoline synthesis 3.1.2 Gen
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3.1 - Oxazoline synthesis mCPBA O N
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3.1 - Oxazoline synthesis 3.1.4.b M
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3.1 - Oxazoline synthesis Ph Ph Ph
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3.2 - Oxazoline removal O N O OH 3N
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3.2 - Oxazoline removal O Me O N OM
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3.2 - Oxazoline removal However, th
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3.2 - Oxazoline removal 3.2.3 Reduc
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3.2 - Oxazoline removal Ph O N Ph P
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3.2 - Oxazoline removal 3.2.3.c Ami
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3.2 - Oxazoline removal Ph Ph Ph Ph
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3.2 - Oxazoline removal 3.2.5.b N-A
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3.2 - Oxazoline removal Ph Ph O N H
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3.2 - Oxazoline removal Ph Me Ph Me
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3.2 - Oxazoline removal 3.2.6 Deter
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Better, however, would be a method
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4.1 - Introduction HO OH OH HO OH O
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4.1 - Introduction (-)-Shikimic aci
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4.1 - Introduction followed by Flem
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4.2 - Carbasugar synthesis 4.2 Synt
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4.2 - Carbasugar synthesis stereoce
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4.2 - Carbasugar synthesis of the o
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4.2 - Carbasugar synthesis support
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4.2 - Carbasugar synthesis Ox* Ox*
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4.2 - Carbasugar synthesis OsO 4 (c
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4.2 - Carbasugar synthesis taken on
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4.2 - Carbasugar synthesis As well
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4.4 - Revised altrose synthesis 4.4
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4.4 - Revised altrose synthesis suf
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4.4 - Revised altrose synthesis ind
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4.5 - Mannose synthesis 4.5 Synthes
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4.5 - Mannose synthesis It is clear
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4.5 - Mannose synthesis considering
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4.5 - Mannose synthesis which would
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4.5 - Mannose synthesis One clear a
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4.5 - Mannose synthesis 4.5.2.b Epo
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4.5 - Mannose synthesis hydrolysis
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4.5 - Mannose synthesis The second
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4.6 - Summary 4.6 Summary & Future
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4.6 - Summary OH CDI, NH 2 OH.HCl,
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184
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References (37) Rawson, D. J.; Meye
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References (105) Gajewski, J. J.; B
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References (169) McCormick, J. P.;
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References 192
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Experimental section 254nm, dodecam
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Experimental section General Proced
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Experimental for chapter 2 Synthesi
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Experimental for chapter 2 (CDCl 3
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Experimental for chapter 2 3H, OMe
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Experimental for chapter 2 Ph), 139
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Experimental for chapter 2 H4), 5.2
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Experimental for chapter 2 108 R f
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Experimental for chapter 2 Synthesi
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Experimental for chapter 3.1 satura
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Experimental for chapter 3.1 Na 2 S
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Experimental for chapter 3.1 Synthe
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Experimental for chapter 3.1 128.9,
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Experimental for chapter 3.1 Microw
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Experimental for chapter 3.1 R f :
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Experimental for chapter 4.1 281 R
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Experimental for chapter 4.1 combin
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Experimental for chapter 4.1 3H, OB
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Experimental for chapter 4.2 (1S*,2
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Experimental for chapter 4.2 10.0,
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Experimental for chapter 4.2 cm 3 )
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Experimental for chapter 4.2 5.7 Re
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Absolute structure parameter 1.3(11
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_diffrn_standards_interval_time ? _
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H13 H 0.8405 0.7136 -0.0889 0.026 U
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C4 C5 1.454(2) . ? C5 C6 1.324(2) .
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C24 C23 C22 120.0(2) . . ? C24 C23
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. Compound 102c Ph O N Ph Me 102c O
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_diffrn_standards_interval_time ? _
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H11 H 0.8924 0.9592 0.6829 0.022 Ui
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C2 H2 1.0000 . ? C3 C21 1.506(2) .
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C26 C21 C3 121.41(15) . . ? C23 C22
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c. Compound 213 Ph O N Ph Me OH 213
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_cell_volume 1080.9(4) _cell_formul
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_refine_ls_number_reflns 4736 _refi
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H25 H 0.7979 0.2335 0.3365 0.028 Ui
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C4 0.025(4) 0.019(4) 0.018(4) 0.001
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loop_ _geom_bond_atom_site_label_1
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C9 C4 C1 107.1(5) . . ? C10 C4 C1 1
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C36 C38 H38A 109.5 . . ? C36 C38 H3
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C29 C30 C36 C37 -90.4(7) . . . . ?
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The structure was solved by the dir
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_reflns_number_total 2447 _reflns_n
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C7 C 1.1671(4) 0.7629(7) 1.2254(4)
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C3 0.015(3) 0.016(3) 0.021(3) -0.00
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C21 H21A 0.9800 . ? C21 H21B 0.9800
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H21A C21 H21C 109.5 . . ? H21B C21
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