Enantioselective synthesis of hindered cyclic dialkyl ethers via catalytic oxa-Michael/Michael desymmetrization.
Corbett, Michael T.; Johnson, Jeffrey S.; Chemical science (Royal Society of Chemistry : 2010) 4 (2013) 2828–2832; doi:10.1039/C3SC51022K

data_1514510
_publ_section_title
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 Enantioselective synthesis of hindered cyclic dialkyl ethers via
 catalytic oxa-Michael/Michael desymmetrization.
;
_journal_issue                   7
_journal_name_full
'Chemical science (Royal Society of Chemistry : 2010)'
_journal_page_first              2828
_journal_page_last               2832
_journal_paper_doi               10.1039/C3SC51022K
_journal_volume                  4
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H21 N O6'
_chemical_formula_sum            'C23 H21 N O6'
_chemical_formula_weight         407.41
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2012-12-19
_audit_creation_method
;
Olex2 1.2-beta
(compiled Dec 5 2012 16:17:34, GUI svn.r4385)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 103.8170(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   16.5029(2)
_cell_length_b                   7.00040(10)
_cell_length_c                   17.5337(2)
_cell_measurement_reflns_used    9821
_cell_measurement_temperature    100
_cell_measurement_theta_max      70.04
_cell_measurement_theta_min      5.20
_cell_volume                     1967.00(4)
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
olex2.solve (L.J. Bourhis, O.V. Dolomanov, R.J. Gildea, J.A.K. Howard,
H. Puschmann, in preparation, 2011)
;
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0224
_diffrn_reflns_av_unetI/netI     0.0209
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            23188
_diffrn_reflns_theta_full        70.04
_diffrn_reflns_theta_max         70.04
_diffrn_reflns_theta_min         2.60
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.829
_exptl_absorpt_correction_T_max  0.9283
_exptl_absorpt_correction_T_min  0.7782
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0444 before and 0.0344 after correction.
The Ratio of minimum to maximum transmission is 0.8383.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.376
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             856
_exptl_crystal_size_max          0.408
_exptl_crystal_size_mid          0.318
_exptl_crystal_size_min          0.124
_refine_diff_density_max         0.193
_refine_diff_density_min         -0.187
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.05(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     543
_refine_ls_number_reflns         7355
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0304
_refine_ls_R_factor_gt           0.0294
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0452P)^2^+0.3154P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0744
_refine_ls_wR_factor_ref         0.0754
_reflns_number_gt                7159
_reflns_number_total             7355
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c3sc51022k.txt
_cod_data_source_block           x1212018
_cod_database_code               1514510
_olex2_refinement_description
;
1. Fixed Uiso
At 1.2 times of:
H2 of C2, H45 of C45, H44 of C44, H43 of C43, H42 of C42, H41 of C41, H39
of C39, {H38A,H38B} of C38, H36 of C36, H35 of C35, H33 of C33, H32 of C32,
{H31A,H31B} of C31, H29 of C29, H28 of C28, H26 of C26, H25 of C25, H3 of C3,
H5 of C5, H6 of C6, {H8A,H8B} of C8, H9 of C9, H10 of C10, H12 of C12, H13 of
C13, {H15A,H15B} of C15, H16 of C16, H18 of C18, H19 of C19, H20 of C20, H21
of C21, H22 of C22
At 1.5 times of:
{H46A,H46B,H46C} of C46, {H23A,H23B,H23C} of C23
2.a Ternary CH refined with riding coordinates:
C9(H9), C10(H10), C16(H16), C32(H32), C33(H33), C39(H39)
2.b Secondary CH2 refined with riding coordinates:
C8(H8A,H8B), C15(H15A,H15B), C31(H31A,H31B), C38(H38A,H38B)
2.c Aromatic/amide H refined with riding coordinates:
C2(H2), C3(H3), C5(H5), C6(H6), C12(H12), C13(H13), C18(H18), C19(H19),
C20(H20), C21(H21), C22(H22), C25(H25), C26(H26), C28(H28), C29(H29), C35(H35),
C36(H36), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45)
2.d Idealised Me refined as rotating group:
C23(H23A,H23B,H23C), C46(H46A,H46B,H46C)
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