Regio- and stereoselective base-catalyzed assembly of 6-methylene-5-oxaspiro[2.4]heptanones from alkynyl cyclopropyl ketones
Samultceva, Sofia O.; Dvorko, Marina Yu.; Shabalin, Dmitrii A.; Ushakov, Igor’ A.; Vashchenko, Alexander V.; Schmidt, Elena Yu.; Trofimov, Boris A.; Organic & Biomolecular Chemistry 20 (2022) 5325–5333; doi:10.1039/D2OB00854H

data_1567143
_publ_section_title
;
 Regio- and stereoselective base-catalyzed assembly of
 6-methylene-5-oxaspiro[2.4]heptanones from alkynyl cyclopropyl ketones
;
_journal_issue                   26
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_page_first              5325
_journal_page_last               5333
_journal_paper_doi               10.1039/D2OB00854H
_journal_volume                  20
_journal_year                    2022
_chemical_formula_moiety         'C24 H18 Br2 O2'
_chemical_formula_sum            'C24 H18 Br2 O2'
_chemical_formula_weight         498.20
_chemical_name_systematic
(Z)-6-(4-Bromobenzylidene)-4-((4-bromophenyl)ethynyl)-4-cyclopropyl-5-oxaspiro[2.4]heptan-7-one
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-03-15
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-03-17 deposited with the CCDC.	2022-06-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 119.385(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.087(3)
_cell_length_b                   24.117(7)
_cell_length_c                   10.137(3)
_cell_measurement_reflns_used    1290
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      23.8
_cell_measurement_theta_min      2.4
_cell_volume                     2148.7(11)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\w and \f'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0956
_diffrn_reflns_av_unetI/netI     0.1362
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            19405
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.799
_diffrn_reflns_theta_min         2.456
_exptl_absorpt_coefficient_mu    3.789
_exptl_absorpt_correction_T_max  0.0788
_exptl_absorpt_correction_T_min  0.0448
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1555 before and 0.0804 after correction.
The Ratio of minimum to maximum transmission is 0.5685.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.540
_exptl_crystal_description       prism
_exptl_crystal_F_000             992
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: methanol'
_exptl_crystal_size_max          0.338
_exptl_crystal_size_mid          0.255
_exptl_crystal_size_min          0.239
_refine_diff_density_max         0.443
_refine_diff_density_min         -0.376
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     261
_refine_ls_number_reflns         4568
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.1971
_refine_ls_R_factor_gt           0.0694
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0411P)^2^+0.7995P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1007
_refine_ls_wR_factor_ref         0.1270
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2021
_reflns_number_total             4568
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob00854h2.cif
_cod_data_source_block           c4
_cod_database_code               1567143
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.465
_shelx_estimated_absorpt_t_min   0.361
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C20(H20)
2.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C19(H19A,H19B), C21(H21A,H21B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C11(H11), C12(H12), C14(H14), C15(H15), C23(H23),
 C24(H24)
;
_shelx_res_checksum              99167
_olex2_submission_special_instructions 'No special instructions were received'