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

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_refine_ls_restrained_S_all 1.154 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group O1 O 1.2534(3) 0.8414(5) 1.1873(2) 0.0274(9) Uani 1 1 d . . . H1 H 1.3159 0.8625 1.2323 0.041 Uiso 1 1 calc R . . O2 O 0.7867(3) 0.6097(4) 1.2036(3) 0.0189(8) Uani 1 1 d . . . H2 H 0.7921 0.5052 1.2085 0.028 Uiso 1 1 calc R . . O3 O 0.7790(3) 0.6641(4) 1.0083(2) 0.0198(8) Uani 1 1 d . . . H3 H 0.7053 0.6879 0.9927 0.030 Uiso 1 1 calc R . . O4 O 0.8975(3) 0.9572(4) 0.9708(2) 0.0228(8) Uani 1 1 d . . . H4 H 0.8385 0.9090 0.9325 0.034 Uiso 1 1 calc R . . O5 O 0.9383(3) 1.1074(4) 1.1463(2) 0.0181(8) Uani 1 1 d . . . H5 H 0.9076 1.1543 1.0930 0.027 Uiso 1 1 calc R . . C1 C 1.0655(4) 0.8838(6) 1.2325(3) 0.0150(11) Uani 1 1 d . . . C2 C 0.9646(4) 0.7839(6) 1.2604(3) 0.0169(11) Uani 1 1 d . . . H2A H 0.9076 0.8709 1.2707 0.020 Uiso 1 1 calc R . . C3 C 0.8888(4) 0.6744(6) 1.1774(3) 0.0160(11) Uani 1 1 d . . . H3A H 0.9391 0.5790 1.1668 0.019 Uiso 1 1 calc R . . C4 C 0.8435(4) 0.7719(6) 1.0851(3) 0.0152(11) Uani 1 1 d . . . H4A H 0.7867 0.8598 1.0947 0.018 Uiso 1 1 calc R . . C5 C 0.9429(4) 0.8564(6) 1.0555(3) 0.0189(12) Uani 1 1 d . . . H5A H 0.9979 0.7692 1.0424 0.023 Uiso 1 1 calc R . . C6 C 1.0152(4) 0.9726(6) 1.1341(3) 0.0159(10) Uani 1 1 d . . . H6 H 1.0839 1.0201 1.1139 0.019 Uiso 1 1 calc R . . 327
C7 C 1.1671(4) 0.7629(7) 1.2254(4) 0.0242(12) Uani 1 1 d . . . H7A H 1.2084 0.7187 1.2905 0.029 Uiso 1 1 calc R . . H7B H 1.1309 0.6671 1.1838 0.029 Uiso 1 1 calc R . . C8 C 1.1195(4) 1.0188(6) 1.3087(3) 0.0199(12) Uani 1 1 d . . . H8A H 1.0544 1.0848 1.3210 0.030 Uiso 1 1 calc R . . H8B H 1.1722 1.0922 1.2848 0.030 Uiso 1 1 calc R . . H8C H 1.1664 0.9651 1.3686 0.030 Uiso 1 1 calc R . . C9 C 1.0102(5) 0.6905(6) 1.3590(3) 0.0200(12) Uani 1 1 d . . . H9 H 1.0862 0.7472 1.3965 0.024 Uiso 1 1 calc R . . C10 C 1.0415(4) 0.5043(7) 1.3499(3) 0.0231(12) Uani 1 1 d . . . H10A H 0.9672 0.4406 1.3230 0.035 Uiso 1 1 calc R . . H10B H 1.0842 0.4602 1.4138 0.035 Uiso 1 1 calc R . . H10C H 1.0930 0.4943 1.3072 0.035 Uiso 1 1 calc R . . C11 C 0.9215(5) 0.7050(7) 1.4181(3) 0.0289(14) Uani 1 1 d . . . H11A H 0.9549 0.6495 1.4805 0.043 Uiso 1 1 calc R . . H11B H 0.8452 0.6517 1.3833 0.043 Uiso 1 1 calc R . . H11C H 0.9073 0.8233 1.4287 0.043 Uiso 1 1 calc R . . O6 O 0.5233(3) 0.4657(4) 0.7296(2) 0.0178(8) Uani 1 1 d . . . H6A H 0.5004 0.3934 0.7625 0.027 Uiso 1 1 calc R . . O7 O 0.6153(3) 0.9803(4) 0.8264(2) 0.0183(8) Uani 1 1 d . . . H7 H 0.5740 1.0656 0.8285 0.027 Uiso 1 1 calc R . . O8 O 0.5623(3) 0.8147(4) 0.9779(2) 0.0154(7) Uani 1 1 d . . . H8 H 0.5943 0.9097 0.9890 0.023 Uiso 1 1 calc R . . O9 O 0.3635(3) 0.6085(4) 0.9470(2) 0.0147(8) Uani 1 1 d . . . H9A H 0.3120 0.6807 0.9497 0.022 Uiso 1 1 calc R . . O10 O 0.2212(3) 0.7613(4) 0.7757(2) 0.0151(7) Uani 1 1 d . . . H10 H 0.1677 0.7116 0.7937 0.023 Uiso 1 1 calc R . . C12 C 0.3608(4) 0.6857(6) 0.6852(3) 0.0164(11) Uani 1 1 d . . . C13 C 0.4427(4) 0.8464(6) 0.7063(3) 0.0152(11) Uani 1 1 d . . . H13 H 0.3883 0.9411 0.7107 0.018 Uiso 1 1 calc R . . C14 C 0.5389(4) 0.8370(6) 0.8059(3) 0.0172(11) Uani 1 1 d . . . H14 H 0.5903 0.7365 0.8063 0.021 Uiso 1 1 calc R . . C15 C 0.4759(4) 0.8137(6) 0.8835(3) 0.0130(10) Uani 1 1 d . . . H15 H 0.4162 0.9058 0.8790 0.016 Uiso 1 1 calc R . . C16 C 0.4122(4) 0.6481(6) 0.8703(3) 0.0148(11) Uani 1 1 d . . . H16 H 0.4728 0.5601 0.8690 0.018 Uiso 1 1 calc R . . C17 C 0.3148(4) 0.6441(6) 0.7724(3) 0.0132(11) Uani 1 1 d . . . H17 H 0.2789 0.5295 0.7628 0.016 Uiso 1 1 calc R . . 328
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Dearomatising Addition of Organolit
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2.3 Synthetic Scope 64 2.3.1 Organo
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Abstract Dearomatising Addition of
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The Author The Author graduated fro
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Abbreviations & Conventions Ac acet
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RDS rate determining step R f RC rt
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Chapter 1: Introduction Chapter 1 -
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Chapter 1: Introduction controlled
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Chapter 1: Introduction diastereome
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Chapter 1: Introduction combine mor
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Chapter 1: Introduction O Ar Cl TMP
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Chapter 1: Introduction conditions,
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Chapter 1: Introduction chiral oxaz
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Chapter 1: Introduction Again a lar
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Chapter 1: Introduction 34 Scheme 1
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Chapter 1: Introduction The amino a
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Chapter 1: Introduction It was envi
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Chapter 1: Introduction COR' i) ATP
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Chapter 1: Introduction O i) ATPH,
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Chapter 1: Introduction 1.4 Nucleop
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Chapter 1: Introduction Unlike the
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Chapter 1: Introduction Diene (-)-8
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Chapter 1: Introduction A scheme su
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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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Page 285 and 286: Absolute structure parameter 1.3(11
Page 287 and 288: _diffrn_standards_interval_time ? _
Page 289 and 290: H13 H 0.8405 0.7136 -0.0889 0.026 U
Page 291 and 292: C4 C5 1.454(2) . ? C5 C6 1.324(2) .
Page 293 and 294: C24 C23 C22 120.0(2) . . ? C24 C23
Page 295 and 296: . Compound 102c Ph O N Ph Me 102c O
Page 297 and 298: _diffrn_standards_interval_time ? _
Page 299 and 300: H11 H 0.8924 0.9592 0.6829 0.022 Ui
Page 301 and 302: C2 H2 1.0000 . ? C3 C21 1.506(2) .
Page 303 and 304: C26 C21 C3 121.41(15) . . ? C23 C22
Page 305 and 306: c. Compound 213 Ph O N Ph Me OH 213
Page 307 and 308: _cell_volume 1080.9(4) _cell_formul
Page 309 and 310: _refine_ls_number_reflns 4736 _refi
Page 311 and 312: H25 H 0.7979 0.2335 0.3365 0.028 Ui
Page 313 and 314: C4 0.025(4) 0.019(4) 0.018(4) 0.001
Page 315 and 316: loop_ _geom_bond_atom_site_label_1
Page 317 and 318: C9 C4 C1 107.1(5) . . ? C10 C4 C1 1
Page 319 and 320: C36 C38 H38A 109.5 . . ? C36 C38 H3
Page 321 and 322: C29 C30 C36 C37 -90.4(7) . . . . ?
Page 323 and 324: The structure was solved by the dir
Page 325: _reflns_number_total 2447 _reflns_n
Page 329 and 330: C3 0.015(3) 0.016(3) 0.021(3) -0.00
Page 331 and 332: C21 H21A 0.9800 . ? C21 H21B 0.9800
Page 333 and 334: H21A C21 H21C 109.5 . . ? H21B C21
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