Ti-Catalyzed Radical Alkylation of Secondary and Tertiary Alkyl Chlorides Using Michael Acceptors.
Wu, Xiangyu; Hao, Wei; Ye, Ke-Yin; Jiang, Binyang; Pombar, Gisselle; Song, Zhidong; Lin, Song; Journal of the American Chemical Society 140 (2018) 14836–14843; doi:10.1021/jacs.8b08605

data_4133132
_publ_section_title
;
 Ti-Catalyzed Radical Alkylation of Secondary and Tertiary Alkyl Chlorides
 Using Michael Acceptors.
;
_journal_issue                   44
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14836
_journal_page_last               14843
_journal_paper_doi               10.1021/jacs.8b08605
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C24 H29 N O5 S'
_chemical_formula_sum            'C24 H29 N O5 S'
_chemical_formula_weight         443.54
_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
_audit_creation_date             2018-03-29
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2016.08.26 svn.r3337 for Rigaku Oxford Diffraction, GUI svn.r5221)
;
_cell_angle_alpha                80.5240(10)
_cell_angle_beta                 74.4700(10)
_cell_angle_gamma                72.2380(10)
_cell_formula_units_Z            2
_cell_length_a                   8.98590(10)
_cell_length_b                   10.71110(10)
_cell_length_c                   12.6455(2)
_cell_measurement_reflns_used    34585
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.7050
_cell_measurement_theta_min      3.6290
_cell_volume                     1112.21(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -71.00 -27.00   0.50    0.25    --  -48.42 -77.00-120.00   88
  2  \w    -62.00 -36.00   0.50    0.25    --  -48.42 -47.00-123.63   52
  3  \w    -71.00 -27.00   0.50    0.25    --  -48.42 -77.00-150.00   88
  4  \w    -90.00 -28.00   0.50    0.25    --  -48.42 -77.00 -60.00  124
  5  \w    -54.00 -29.00   0.50    0.25    --  -48.42 -77.00 -30.00   50
  6  \w    -55.00 -27.00   0.50    0.25    --  -48.42 -77.00  30.00   56
  7  \w    -71.00 -27.00   0.50    0.25    --  -48.42 -77.00 150.00   88
  8  \w    -92.00 -67.00   0.50    1.01    --  -86.25 -71.00  97.38   50
  9  \w    -92.00 -66.00   0.50    1.01    --  -86.25 -72.00 149.43   52
 10  \w    -97.00 -66.00   0.50    1.01    --  -86.25 -72.00 127.76   62
 11  \w    -90.00 -65.00   0.50    1.01    --  -86.25 -76.00 114.36   50
 12  \w    -88.00 -62.00   0.50    1.01    --  -86.25 -83.00  56.29   52
 13  \w    -89.00 -64.00   0.50    1.01    --  -86.25 -77.00  30.00   50
 14  \w    -90.00 -64.00   0.50    1.01    --  -86.25 -82.00 -23.06   52
 15  \w    -88.00 -62.00   0.50    1.01    --  -86.25 -83.00  26.83   52
 16  \w    -89.00 -62.00   0.50    1.01    --  -86.25 -83.00 -35.38   54
 17  \w    -89.00 -64.00   0.50    1.01    --  -86.25 -77.00   0.00   50
 18  \w    -92.00 -66.00   0.50    1.01    --  -86.25 -73.00  62.12   52
 19  \w    -91.00 -65.00   0.50    1.01    --  -86.25 -75.00 125.92   52
 20  \w    -89.00 -64.00   0.50    1.01    --  -86.25 -77.00  88.06   50
 21  \w   -119.00 -70.00   0.50    0.25    --  -48.42-125.00 152.00   98
 22  \w   -119.00 -27.00   0.50    0.25    --  -48.42 -77.00  90.00  184
 23  \w   -110.00 -37.00   0.50    0.25    --  -48.42 -37.00  30.00  146
 24  \w   -106.00 -64.00   0.50    1.01    --  -86.25 -79.00 -10.61   84
 25  \w    -97.00 -65.00   0.50    1.01    --  -86.25 -76.00 -99.32   64
 26  \w    -90.00 -64.00   0.50    1.01    --  -86.25 -77.00-120.00   52
 27  \w    -93.00 -63.00   0.50    1.01    --  -86.25 -81.00-132.87   60
 28  \w    -92.00 -67.00   0.50    1.01    --  -86.25 -70.00-167.31   50
 29  \w    -97.00 -64.00   0.50    1.01    --  -86.25 -77.00-180.00   66
 30  \w   -111.00 -67.00   0.50    0.25    --  -48.42 -47.00-123.63   88
 31  \w   -111.00 -66.00   0.50    1.01    --  -86.25 -72.00 -82.39   90
 32  \w    -97.00 -64.00   0.50    1.01    --  -86.25 -77.00 -60.00   66
 33  \w   -119.00 -57.00   0.50    0.25    --  -48.42-145.00 -15.00  124
 34  \w   -119.00 -93.00   0.50    0.25    --  -48.42 -77.00  30.00   52
 35  \w   -112.00 -38.00   0.50    0.25    --  -48.42 -43.00 -30.33  148
 36  \w   -119.00 -93.00   0.50    0.25    --  -48.42 -77.00-150.00   52
 37  \w   -135.00-109.00   0.50    1.01    --  -86.25 -77.00-180.00   52
 38  \w   -158.00 -57.00   0.50    1.01    --  -86.25-145.00 -15.00  202
 39  \w   -117.00 -92.00   0.50    0.25    --  -48.42 -77.00 150.00   50
 40  \w   -158.00 -70.00   0.50    1.01    --  -86.25-125.00 152.00  176
 41  \w   -145.00-119.00   0.50    1.01    --  -86.25 -83.00 -35.38   52
 42  \w     28.00  54.00   0.50    0.25    --   48.42  77.00 120.00   52
 43  \w     39.00  66.00   0.50    0.25    --   48.42  37.00 150.00   54
 44  \w     79.00 120.00   0.50    0.25    --   48.42  19.00 120.00   82
 45  \w    138.00 164.00   0.50    1.01    --  107.75  61.00  90.00   52
 46  \w    153.00 178.00   0.50    1.01    --  107.75  30.00 150.00   50
 47  \w    139.00 165.00   0.50    1.01    --  107.75  77.00 120.00   52
 48  \w    136.00 166.00   0.50    1.01    --  107.75  61.00 120.00   60
 49  \w    137.00 178.00   0.50    1.01    --  107.75  77.00  30.00   82
 50  \w    142.00 174.00   0.50    1.01    --  107.75  77.00   0.00   64
 51  \w    138.00 178.00   0.50    1.01    --  107.75  77.00 -60.00   80
 52  \w    129.00 172.00   0.50    1.01    --  107.75  77.00-150.00   86
 53  \w    141.00 166.00   0.50    1.01    --  107.75  45.00-150.00   50
 54  \w    127.00 169.00   0.50    1.01    --  107.75  61.00 -90.00   84
 55  \w    127.00 153.00   0.50    1.01    --  107.75  77.00 -30.00   52
 56  \w    118.00 143.00   0.50    1.01    --  107.75  45.00   0.00   50
 57  \w    102.00 145.00   0.50    1.01    --  107.75  61.00  30.00   86
 58  \w    104.00 165.00   0.50    1.01    --  107.75  30.00   0.00  122
 59  \w     97.00 144.00   0.50    1.01    --  107.75  61.00 -30.00   94
 60  \w     92.00 178.00   0.50    1.01    --  107.75 125.00-130.00  172
 61  \w    106.00 155.00   0.50    1.01    --  107.75  30.00-180.00   98
 62  \w    100.00 136.00   0.50    1.01    --  107.75  45.00-150.00   72
 63  \w     93.00 161.00   0.50    1.01    --  107.75  61.00-180.00  136
 64  \w     98.00 158.00   0.50    1.01    --  107.75  61.00 -60.00  120
 65  \w     94.00 150.00   0.50    1.01    --  107.75  61.00  60.00  112
 66  \w     93.00 130.00   0.50    1.01    --  107.75  61.00  90.00   74
 67  \w    100.00 137.00   0.50    1.01    --  107.75  30.00 150.00   74
 68  \w     97.00 178.00   0.50    1.01    --  107.75  15.00 120.00  162
 69  \w    101.00 126.00   0.50    1.01    --  107.75 -77.00   0.00   50
 70  \w     85.00 115.00   0.50    1.01    --  107.75-125.00  30.00   60
 71  \w     84.00 116.00   0.50    1.01    --  107.75-125.00   0.00   64
 72  \w     72.00 109.00   0.50    1.01    --  107.75 -94.00 -60.00   74
 73  \w     63.00 113.00   0.50    1.01    --  107.75-125.00-120.00  100
 74  \w     83.00 116.00   0.50    1.01    --  107.75-125.00-180.00   66
 75  \w     97.00 122.00   0.50    1.01    --  107.75 -61.00-180.00   50
 76  \w     72.00  99.00   0.50    1.01    --  107.75 -58.00-175.16   54
 77  \w     49.00  77.00   0.50    1.01    --  107.75 -45.00-180.00   56
 78  \w     36.00  62.00   0.50    1.01    --  107.75 -61.00-180.00   52
 79  \w     38.00 108.00   0.50    1.01    --  107.75 -94.00-180.00  140
 80  \w     64.00 104.00   0.50    1.01    --  107.75 -65.00 -49.13   80
 81  \w     75.00 119.00   0.50    1.01    --  107.75 -61.00  30.00   88
 82  \w     78.00 111.00   0.50    1.01    --  107.75-106.00  81.46   66
 83  \w     93.00 119.00   0.50    1.01    --  107.75 -65.00 125.78   52
 84  \w     89.00 130.00   0.50    1.01    --  107.75 -77.00 150.00   82
 85  \w     77.00 116.00   0.50    1.01    --  107.75-125.00  90.00   78
 86  \w     83.00 108.00   0.50    1.01    --  107.75 -94.00  90.00   50
 87  \w     57.00 106.00   0.50    1.01    --  107.75 -77.00  17.83   98
 88  \w     51.00 116.00   0.50    1.01    --  107.75-125.00 -30.00  130
 89  \w     42.00 107.00   0.50    0.25    --   48.42-145.00 -15.00  130
 90  \w     42.00 131.00   0.50    1.01    --  107.75-145.00 -15.00  178
 91  \w     36.00 116.00   0.50    1.01    --  107.75-125.00 152.00  160
 92  \w     43.00  68.00   0.50    1.01    --  107.75 -77.00 150.00   50
 93  \w     37.00  73.00   0.50    1.01    --  107.75 -65.00 125.78   72
 94  \w     42.00  70.00   0.50    1.01    --  107.75-106.00  81.46   56
 95  \w     39.00  72.00   0.50    1.01    --  107.75-125.00  90.00   66
 96  \w     45.00  79.00   0.50    1.01    --  107.75-125.00  30.00   68
 97  \w     36.00  66.00   0.50    1.01    --  107.75 -94.00  90.00   60
 98  \w     38.00  85.00   0.50    1.01    --  107.75 -17.00 176.95   94
 99  \w     36.00  64.00   0.50    1.01    --  107.75 -30.00 150.00   56
100  \w    105.00 153.00   0.50    1.01    --  107.75  45.00  60.00   96
101  \w     96.00 152.00   0.50    1.01    --  107.75  61.00 150.00  112
102  \w     87.00 117.00   0.50    1.01    --  107.75  77.00  60.00   60
103  \w     86.00 121.00   0.50    1.01    --  107.75  77.00   0.00   70
104  \w     93.00 170.00   0.50    1.01    --  107.75  61.00   0.00  154
105  \w     87.00 112.00   0.50    1.01    --  107.75  77.00 150.00   50
106  \w     93.00 125.00   0.50    1.01    --  107.75  61.00 120.00   64
107  \w     86.00 112.00   0.50    1.01    --  107.75  77.00 120.00   52
108  \w     86.00 153.00   0.50    1.01    --  107.75  77.00  90.00  134
109  \w     86.00 126.00   0.50    1.01    --  107.75  77.00  30.00   80
110  \w     88.00 119.00   0.50    1.01    --  107.75  77.00 -30.00   62
111  \w     89.00 124.00   0.50    1.01    --  107.75  77.00 -60.00   70
112  \w     93.00 178.00   0.50    1.01    --  107.75  61.00-120.00  170
113  \w     86.00 122.00   0.50    1.01    --  107.75  77.00-150.00   72
114  \w     93.00 154.00   0.50    1.01    --  107.75  61.00-150.00  122
115  \w     86.00 112.00   0.50    1.01    --  107.75  77.00-180.00   52
116  \w     87.00 126.00   0.50    1.01    --  107.75  77.00-120.00   78
117  \w     86.00 137.00   0.50    1.01    --  107.75  77.00 -90.00  102
118  \w     94.00 119.00   0.50    1.01    --  107.75  61.00 -90.00   50
119  \w     78.00 174.00   0.50    1.01    --  107.75 145.00  36.00  192
120  \w     71.00 100.00   0.50    0.25    --   48.42  19.00 -90.00   58
121  \w     41.00  70.00   0.50    0.25    --   48.42  19.00 -90.00   58
122  \w     36.00  77.00   0.50    1.01    --  107.75 -46.00 -62.25   82
123  \w     36.00  77.00   0.50    1.01    --  107.75 -94.00 -30.00   82
124  \w     38.00  77.00   0.50    1.01    --  107.75 -77.00   0.00   78
125  \w     37.00  67.00   0.50    1.01    --  107.75 -30.00  30.00   60
126  \w     35.00  69.00   0.50    1.01    --  107.75 -30.00 -30.00   68
127  \w     41.00  77.00   0.50    1.01    --  107.75 -45.00-120.00   72
128  \w     38.00  74.00   0.50    1.01    --  107.75-125.00-180.00   72
129  \w     45.00  71.00   0.50    0.25    --   48.42  19.00 120.00   52
130  \w     31.00  95.00   0.50    0.25    --   48.42-125.00 152.00  128
131  \w    -91.00 -10.00   0.50    0.25    --  -48.42 125.00-130.00  162
132  \w    -91.00 -14.00   0.50    1.01    --  -86.25 125.00-130.00  154
133  \w   -106.00 -20.00   0.50    0.25    --  -48.42 145.00  36.00  172
134  \w   -106.00 -20.00   0.50    1.01    --  -86.25 145.00  36.00  172
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0763482000
_diffrn_orient_matrix_UB_12      0.0030129000
_diffrn_orient_matrix_UB_13      0.1244475000
_diffrn_orient_matrix_UB_21      0.1347418000
_diffrn_orient_matrix_UB_22      -0.1225745000
_diffrn_orient_matrix_UB_23      0.0235963000
_diffrn_orient_matrix_UB_31      0.1012919000
_diffrn_orient_matrix_UB_32      0.0892402000
_diffrn_orient_matrix_UB_33      0.0087014000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0266
_diffrn_reflns_av_unetI/netI     0.0123
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            45739
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.486
_diffrn_reflns_theta_min         3.643
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.590
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.747
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.45g (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_density_diffrn    1.324
_exptl_crystal_description       block
_exptl_crystal_F_000             472
_exptl_crystal_size_max          0.176
_exptl_crystal_size_mid          0.119
_exptl_crystal_size_min          0.091
_refine_diff_density_max         0.373
_refine_diff_density_min         -0.387
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     405
_refine_ls_number_reflns         4552
_refine_ls_number_restraints     928
_refine_ls_restrained_S_all      0.987
_refine_ls_R_factor_all          0.0365
_refine_ls_R_factor_gt           0.0354
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0502P)^2^+0.4853P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0980
_refine_ls_wR_factor_ref         0.0991
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4362
_reflns_number_total             4552
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b08605_si_002.cif
_cod_data_source_block           rxw3_abs
_cod_database_code               4133132
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C24H29NO5S
_reflns_odcompleteness_completeness 98.40
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     78.52
_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. Restrained distances
 O4-C20 \\sim O4B-C20B
 with sigma of 0.02
 O5B-C20B \\sim O5-C20
 with sigma of 0.02
 O5B-C21B \\sim O5-C21
 with sigma of 0.02
 C24-C21 \\sim C24B-C21B \\sim C23B-C21B \\sim C22-C21 \\sim C22B-C21B \\sim
C23-C21
 with sigma of 0.02
 C20-C19 \\sim C20B-C19B
 with sigma of 0.02
 C19B-C18B \\sim C19-C18 \\sim C18B-C14B \\sim C18-C14
 with sigma of 0.02
 C14B-C13 \\sim C14-C13
 with sigma of 0.02
 C15-C14B \\sim C15-C14
 with sigma of 0.02
 O3B-C15 \\sim O3-C15
 with sigma of 0.02
 O3B-C16B \\sim O3-C16
 with sigma of 0.02
 C17-C16 \\sim C17B-C16B
 with sigma of 0.02
 C17-C14 \\sim C17B-C14B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O3B)=Sof(O4B)=Sof(O5B)=Sof(H15A)=Sof(C14B)=Sof(C16B)=Sof(H16C)=Sof(H16D)=
 Sof(C17B)=Sof(H17C)=Sof(H17D)=Sof(C18B)=Sof(H18C)=Sof(H18D)=Sof(C19B)=
 Sof(H19C)=Sof(H19D)=Sof(C20B)=Sof(C21B)=Sof(C22B)=Sof(H22D)=Sof(H22E)=
 Sof(H22F)=Sof(C23B)=Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C24B)=Sof(H24D)=
 Sof(H24E)=Sof(H24F)=1-FVAR(1)
 Sof(O3)=Sof(O4)=Sof(O5)=Sof(H15)=Sof(C14)=Sof(C16)=Sof(H16A)=Sof(H16B)=
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(C19)=Sof(H19A)=
 Sof(H19B)=Sof(C20)=Sof(C21)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C23)=
 Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C15(H15), C15(H15A)
6.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C16B(H16C,
 H16D), C17B(H17C,H17D), C18B(H18C,H18D), C19B(H19C,H19D)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12)
6.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C22B(H22D,H22E,H22F), C23B(H23D,H23E,H23F), C24B(H24D,H24E,H24F)
;
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.169
_oxdiff_exptl_absorpt_empirical_full_min 0.898