A Phosphine-Free Manganese Catalyst Enables Stereoselective Synthesis of (1 + n)-Membered Cycloalkanes from Methyl Ketones and 1,n-Diols
Jana, Akash; Das, Kuhali; Kundu, Abhishek; Thorve, Pradip Ramdas; Adhikari, Debashis; Maji, Biplab; ACS Catalysis  (2020) 2615–; doi:10.1021/acscatal.9b05567

data_4517391
_publ_section_title
;
 A Phosphine-Free Manganese Catalyst Enables Stereoselective Synthesis of
 (1 + n)-Membered Cycloalkanes from Methyl Ketones and 1,n-Diols
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              2615
_journal_paper_doi               10.1021/acscatal.9b05567
_journal_year                    2020
_chemical_formula_moiety         'C15 H14 Br Mn N2 O3 S'
_chemical_formula_sum            'C15 H14 Br Mn N2 O3 S'
_chemical_formula_weight         437.19
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-10-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                83.308(4)
_cell_angle_beta                 86.928(4)
_cell_angle_gamma                73.022(5)
_cell_formula_units_Z            2
_cell_length_a                   6.6200(3)
_cell_length_b                   7.8565(5)
_cell_length_c                   17.0496(7)
_cell_measurement_reflns_used    4485
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      65.6300
_cell_measurement_theta_min      2.5990
_cell_volume                     842.15(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33c (release 11-04-2014 CrysAlis171 .NET)
(compiled Apr 11 2014,15:12:41)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33c (release 11-04-2014 CrysAlis171 .NET)
(compiled Apr 11 2014,15:12:41)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33c (release 11-04-2014 CrysAlis171 .NET)
(compiled Apr 11 2014,15:12:41)
;
_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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9580
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_details
;
  1 omega  -50.00   64.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       26.3311  -57.0000    0.0000 114

  2 omega   57.00  121.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       26.3311  178.0000   30.0000 64

  3 omega    1.00   81.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       26.3311  -99.0000 -150.0000 80

  4 omega  -55.00   82.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       26.3311  -38.0000   60.0000 137

  5 omega  -12.00  102.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       26.3311   57.0000 -150.0000 114

  6 omega   20.00  147.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656   45.0000   30.0000 127

  7 omega  -18.00  110.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656  -77.0000 -180.0000 128

  8 omega   57.00  150.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656  178.0000 -120.0000 93

  9 omega   30.00  144.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656   61.0000    0.0000 114

 10 omega   57.00  150.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656  178.0000    0.0000 93

 11 omega  100.00  153.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656  111.0000  150.0000 53

 12 omega  100.00  153.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656  111.0000   90.0000 53

 13 omega   30.00  144.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656   61.0000  120.0000 114

 14 omega  100.00  153.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656  111.0000    0.0000 53

 15 omega   24.00  152.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656   77.0000   60.0000 128

 16 omega   21.00  113.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -104.0000 -120.0000 92

 17 omega  101.00  178.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  104.0000 -180.0000 77

 18 omega   21.00  113.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -104.0000  150.0000 92

 19 omega   31.00  147.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -54.0000 -180.0000 116

 20 omega   31.00  147.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -54.0000   90.0000 116

 21 omega   21.00  113.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -104.0000   30.0000 92

 22 omega   30.00  178.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000   29.0000   27.8200 148

 23 omega   21.00  113.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -104.0000  -30.0000 92

 24 omega   25.00  178.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000   21.0000  -30.0000 153

 25 omega   29.00  145.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -65.0000 -120.0000 116

 26 omega   21.00  178.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -21.0000  -90.0000 157

 27 omega   19.00  158.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -89.0000   90.0000 139

 28 omega   19.00  158.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -89.0000  -30.0000 139

 29 omega   21.00  178.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -21.0000  120.0000 157

 30 omega   19.00  158.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -89.0000  -90.0000 139

 31 omega   21.00  178.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -21.0000   30.0000 157

 32 omega   26.00  120.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -122.0000  127.4754 94

 33 omega  -17.00  111.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       26.3311   77.0000   60.0000 128

 34 omega  -12.00  102.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       26.3311   57.0000  150.0000 114

 35 omega  -17.00  111.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       26.3311   77.0000    0.0000 128

 36 omega  -12.00  102.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       26.3311   57.0000 -120.0000 114

 37 omega  -12.00  102.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       26.3311   57.0000  -30.0000 114

 38 omega   24.00  152.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656   77.0000  -90.0000 128

 39 omega   24.00  152.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656   77.0000    0.0000 128

 40 omega   30.00  144.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656   61.0000 -150.0000 114

 41 omega   24.00  152.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656   77.0000  -60.0000 128

 42 omega  100.00  153.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656  111.0000 -150.0000 53

 43 omega   24.00  152.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656   77.0000  150.0000 128

 44 omega   24.00  152.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656   77.0000  120.0000 128

 45 omega  100.00  153.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656  111.0000 -180.0000 53

 46 omega   24.00  152.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656   77.0000   30.0000 128

 47 omega   24.00  152.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -       67.1656   77.0000 -150.0000 128

 48 omega   65.00  178.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   30.0000 113

 49 omega   65.00  178.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -90.0000 113

 50 omega   65.00  178.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -120.0000 113

 51 omega   65.00  178.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -180.0000 113

 52 omega   65.00  178.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000    0.0000 113

 53 omega   71.00  178.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000   65.0000 -150.0000 107

 54 omega   58.00  178.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000   43.0000  120.0000 120

 55 omega   71.00  178.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000   65.0000   60.0000 107

 56 omega   36.00  178.00   1.0000    7.1700
omega____ theta____ kappa____ phi______ frames
    -      108.0000   32.0000 -180.0000 142
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1468951000
_diffrn_orient_matrix_UB_12      -0.0292277000
_diffrn_orient_matrix_UB_13      0.0704912000
_diffrn_orient_matrix_UB_21      -0.0593687000
_diffrn_orient_matrix_UB_22      -0.1717695000
_diffrn_orient_matrix_UB_23      0.0307550000
_diffrn_orient_matrix_UB_31      0.1847338000
_diffrn_orient_matrix_UB_32      -0.1102255000
_diffrn_orient_matrix_UB_33      -0.0486374000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0485
_diffrn_reflns_av_unetI/netI     0.0413
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            10002
_diffrn_reflns_theta_full        66.35
_diffrn_reflns_theta_max         66.35
_diffrn_reflns_theta_min         5.23
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.446
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71208
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33c (release 11-04-2014 CrysAlis171 .NET)
(compiled Apr 11 2014,15:12:41)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear brownish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.724
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       irregular
_exptl_crystal_F_000             436
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.368
_refine_diff_density_min         -0.503
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.980
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         2891
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.980
_refine_ls_R_factor_all          0.0464
_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
'calc w=1/[\s^2^(Fo^2^)+(0.0561P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0886
_refine_ls_wR_factor_ref         0.0943
_reflns_number_gt                2348
_reflns_number_total             2891
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            cs9b05567_si_003.cif
_cod_data_source_block           aja-ac-069
_cod_original_cell_volume        842.15(7)
_cod_database_code               4517391
_chemical_oxdiff_formula         'C H N Mn S O Br'
_reflns_odcompleteness_completeness 97.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
2.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C6(H6A,H6B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C10(H10), C4(H4), C3(H3), C2(H2), C12(H12), C11(H11)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_olex2_date_sample_data_collection 2019-10-10
_olex2_submission_special_instructions 'No special instructions were received'