Enantioselective Syntheses of Spiroketals via a Tandem Reaction of Cu(I) -Catalyzed Cycloetherification and H-Bond-induced [4 + 2] Cyclization.
Tian, Tian; Li, Liqi; Xue, Jijun; Zhang, Jie; Li, Ying; The Journal of organic chemistry  (2015) 150407100357003–; doi:10.1021/acs.joc.5b00384

data_4030931
_publ_section_title
;
 Enantioselective Syntheses of Spiroketals via a Tandem Reaction of Cu(I)
 -Catalyzed Cycloetherification and H-Bond-induced [4 + 2] Cyclization.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              150407100357003
_journal_paper_doi               10.1021/acs.joc.5b00384
_journal_year                    2015
_chemical_formula_moiety         'C11 H11 Br O3'
_chemical_formula_sum            'C11 H11 Br O3'
_chemical_formula_weight         271.11
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-11-21
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 110.044(7)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   11.7748(8)
_cell_length_b                   5.8863(3)
_cell_length_c                   17.0638(10)
_cell_measurement_reflns_used    1564
_cell_measurement_temperature    294.29(10)
_cell_measurement_theta_max      23.1580
_cell_measurement_theta_min      3.6810
_cell_volume                     1111.06(12)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      294.29(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
'#__ type_ start__ end____ width___ exp.time_ 1 
omega -20.00 9.00 1.0000 10.0000 
omega____ theta____ kappa____ phi______ frames - -16.3571 -99.0000 -150.0000 29 
omega 39.00 90.00 1.0000 10.0000 
omega____ theta____ kappa____ phi______ frames - 19.8727 178.0000 -150.0000 51 
omega -39.00 76.00 1.0000 10.0000 
omega____ theta____ kappa____ phi______ frames - 19.8727 0.0000 -60.0000 115 
omega 12.00 37.00 1.0000 10.0000 
omega____ theta____ kappa____ phi______ frames - 19.8727 -57.0000 0.0000 25 
omega -16.00 10.00 1.0000 10.0000 
omega____ theta____ kappa____ phi______ frames - -16.3571 -99.0000 120.0000 26 
omega -7.00 20.00 1.0000 10.0000 
omega____ theta____ kappa____ phi______ frames - -16.3571 -99.0000 30.0000 27 
omega -17.00 9.00 1.0000 10.0000 
omega____ theta____ kappa____ phi______ frames - -16.3571 -99.0000 -30.0000 26 
omega -6.00 77.00 1.0000 10.0000 
omega____ theta____ kappa____ phi______ frames - 19.7946 38.0000 0.0000 83'
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0008788000
_diffrn_orient_matrix_UB_12      0.0355940000
_diffrn_orient_matrix_UB_13      0.0395002000
_diffrn_orient_matrix_UB_21      -0.0508317000
_diffrn_orient_matrix_UB_22      -0.0705682000
_diffrn_orient_matrix_UB_23      -0.0049890000
_diffrn_orient_matrix_UB_31      0.0390642000
_diffrn_orient_matrix_UB_32      -0.0909966000
_diffrn_orient_matrix_UB_33      0.0193124000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0295
_diffrn_reflns_av_unetI/netI     0.0331
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            7446
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.01
_diffrn_reflns_theta_min         3.62
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.683
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81036
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.621
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             544
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.23
_refine_diff_density_max         0.250
_refine_diff_density_min         -0.319
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     138
_refine_ls_number_reflns         2189
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0623
_refine_ls_R_factor_gt           0.0380
_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^)+(0.0284P)^2^+0.6570P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0746
_refine_ls_wR_factor_ref         0.0830
_reflns_number_gt                1563
_reflns_number_total             2189
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo5b00384_si_004.cif
_cod_data_source_block           tiant1105
_cod_original_cell_volume        1111.05(11)
_cod_database_code               4030931
_reflns_odcompleteness_completeness 99.60
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3), C5(H5), C9(H9)
2.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C)
2.e Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_olex2_submission_special_instructions 'No special instructions were received'