Photoinduced Carboborative Ring Contraction Enables Regio- and Stereoselective Synthesis of Multiply Substituted Five-Membered Carbocycles and Heterocycles.
Jin, Shengfei; Nguyen, Vu T.; Dang, Hang T.; Nguyen, Dat P.; Arman, Hadi D.; Larionov, Oleg V.; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b07128

data_4126328
_publ_section_title
;
 Photoinduced Carboborative Ring Contraction Enables Regio- and
 Stereoselective Synthesis of Multiply Substituted Five-Membered
 Carbocycles and Heterocycles.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b07128
_journal_year                    2017
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C12 H22 O2'
_chemical_formula_sum            'C12 H22 O2'
_chemical_formula_weight         198.29
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-02-07
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.901(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.2193(4)
_cell_length_b                   6.1407(4)
_cell_length_c                   13.5485(7)
_cell_measurement_reflns_used    2629
_cell_measurement_temperature    98
_cell_measurement_theta_max      38.9870
_cell_measurement_theta_min      2.9890
_cell_volume                     599.86(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      98
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -68.00  55.00   0.50   50.00    --  -35.00  70.00   0.00  246
  2  \w    -63.00  42.00   0.50   50.00    --  -35.00  70.00 180.00  210
  3  \w    -80.00 -20.00   0.50   50.00    --  -35.00   0.00 180.00  120
  4  \w    -61.00 -27.00   0.50   50.00    --  -35.00  70.00  90.00   68
  5  \w   -115.00 -85.00   0.50   50.00    --  -35.00   0.00 270.00   60
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0897194000
_diffrn_orient_matrix_UB_12      0.0111477000
_diffrn_orient_matrix_UB_13      -0.0185379000
_diffrn_orient_matrix_UB_21      0.0402537000
_diffrn_orient_matrix_UB_22      -0.0135796000
_diffrn_orient_matrix_UB_23      0.0484296000
_diffrn_orient_matrix_UB_31      0.0038730000
_diffrn_orient_matrix_UB_32      -0.1141321000
_diffrn_orient_matrix_UB_33      -0.0076206000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0175
_diffrn_reflns_av_unetI/netI     0.0200
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            4082
_diffrn_reflns_point_group_measured_fraction_full 0.857
_diffrn_reflns_point_group_measured_fraction_max 0.858
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.499
_diffrn_reflns_theta_min         2.825
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.072
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76273
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.098
_exptl_crystal_description       plate
_exptl_crystal_F_000             220
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.218
_refine_diff_density_min         -0.121
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;

;
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     136
_refine_ls_number_reflns         1921
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0383
_refine_ls_R_factor_gt           0.0368
_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^)+(0.0500P)^2^+0.1500P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0925
_refine_ls_wR_factor_ref         0.0937
_reflns_Friedel_coverage         0.561
_reflns_Friedel_fraction_full    0.683
_reflns_Friedel_fraction_max     0.685
_reflns_number_gt                1873
_reflns_number_total             1921
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07128_si_002.cif
_cod_data_source_block           cd1547
_cod_database_code               4126328
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C12O2H12
_reflns_odcompleteness_completeness 99.93
_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 C(H,H,H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C10(H10), C1(H1A), C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C2(H2A,H2B), C11(H11A,H11B)
2.c X=CH2 refined with riding coordinates:
 C8(H8A,H8B)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C12(H12A,H12B,H12C), C7(H7A,H7B,H7C)
;
_olex2_exptl_crystal_mounting_method 'nylon loop'
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.310
_oxdiff_exptl_absorpt_empirical_full_min 0.818