SmCp<sup>R</sup><sub>2</sub>-mediated cross-coupling of allyl and propargyl ethers with ketoesters and a telescoped approach to complex cycloheptanols.
Plesniak, Mateusz P.; Just-Baringo, Xavier; Ortu, Fabrizio; Mills, David P.; Procter, David J.; Chemical communications (Cambridge, England) 52 (2016) 13503–13506; doi:10.1039/c6cc07318b

data_7125180
_publ_section_title
;
 SmCp<sup>R</sup><sub>2</sub>-mediated cross-coupling of allyl and
 propargyl ethers with ketoesters and a telescoped approach to complex
 cycloheptanols.
;
_journal_issue                   92
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              13503
_journal_page_last               13506
_journal_paper_doi               10.1039/c6cc07318b
_journal_volume                  52
_journal_year                    2016
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C54 H54 O2 Si2 Sm'
_chemical_formula_sum            'C54 H54 O2 Si2 Sm'
_chemical_formula_weight         941.50
_chemical_properties_physical    ', Air-sensitive,Moisture-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-11-13
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-08-29 deposited with the CCDC.
2016-10-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.283(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.1230(6)
_cell_length_b                   9.6421(3)
_cell_length_c                   27.6291(11)
_cell_measurement_reflns_used    17283
_cell_measurement_temperature    120(3)
_cell_measurement_theta_max      26.9120
_cell_measurement_theta_min      4.0010
_cell_volume                     4501.9(3)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      120(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1636
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -17.00  79.00   1.00   15.00    --    8.81  77.00 120.00   96
  2  \w     11.00  86.00   1.00   15.00    --    8.81  19.00  60.00   75
  3  \w    -82.00 -14.00   1.00   15.00    --   -9.28 153.00-164.23   68
  4  \w    -66.00  10.00   1.00   15.00    --   -9.28 -37.00-120.00   76
  5  \w    -77.00  -1.00   1.00   15.00    --   -9.28 -37.00-180.00   76
  6  \w    -34.00  53.00   1.00   15.00    --   -9.28  57.00   0.00   87
  7  \w    -60.00 -18.00   1.00   15.00    --   -9.28 119.00 116.35   42
  8  \w    -68.00 -12.00   1.00   15.00    --   -9.28 132.00  24.60   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0405755000
_diffrn_orient_matrix_UB_12      -0.0163788000
_diffrn_orient_matrix_UB_13      0.0072082000
_diffrn_orient_matrix_UB_21      0.0055432000
_diffrn_orient_matrix_UB_22      0.0018333000
_diffrn_orient_matrix_UB_23      -0.0248887000
_diffrn_orient_matrix_UB_31      0.0091161000
_diffrn_orient_matrix_UB_32      0.0717147000
_diffrn_orient_matrix_UB_33      0.0022907000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1225
_diffrn_reflns_av_unetI/netI     0.0999
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            31392
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.346
_diffrn_reflns_theta_min         3.437
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.398
_exptl_absorpt_correction_T_max  0.863
_exptl_absorpt_correction_T_min  0.705
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.389
_exptl_crystal_description       block
_exptl_crystal_F_000             1936
_exptl_crystal_size_max          0.405
_exptl_crystal_size_mid          0.234
_exptl_crystal_size_min          0.157
_refine_diff_density_max         1.975
_refine_diff_density_min         -1.482
_refine_diff_density_rms         0.151
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     533
_refine_ls_number_reflns         8182
_refine_ls_number_restraints     644
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0726
_refine_ls_R_factor_gt           0.0624
_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^)+(0.0894P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1514
_refine_ls_wR_factor_ref         0.1586
_reflns_Friedel_coverage         0.999
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                7260
_reflns_number_total             8182
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc07318b2.cif
_cod_data_source_block           5f
_cod_database_code               7125180
_manchester_internal_coll_name   odpm34
_manchester_internal_coll_client MP/DJP/DPM
_manchester_internal_coll_type   custom
_manchester_internal_coll_frame_time 15s
_manchester_internal_coll_frame_width 1
_manchester_internal_coll_frame_method '\w scans'
_manchester_internal_coll_user   MP
_manchester_internal_coll_date   28/10/2015
_manchester_internal_process_user FO
_manchester_internal_process_date 13/11/2015
_manchester_internal_solution_user FO
_manchester_internal_solution_date 13/11/2015
_manchester_internal_refinement_user FO
_manchester_internal_refinement_date 13/11/2015
_manchester_internal_validation_user FO
_manchester_internal_validation_date 26/11/2015
_manchester_internal_archive_date 26/11/2015
_chemical_oxdiff_formula         C54H52O2Si2Sm1
_reflns_odcompleteness_completeness 99.63
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.03(3) -0.03(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C3) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.004
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.a Secondary CH2 refined with riding coordinates:
 C47(H47A,H47B), C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,
 H51B), C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11),
 C13(H13), C14(H14), C15(H15), C16(H16), C17(H17), C19(H19), C20(H20), C21(H21),
  C22(H22), C23(H23), C25(H25), C26(H26), C27(H27), C28(H28), C30(H30),
 C31(H31), C32(H32), C33(H33), C34(H34), C36(H36), C37(H37), C38(H38), C39(H39),
  C40(H40), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46)
;
_shelx_res_checksum              17219
_shelx_shelxl_version_number     2014/7
_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 1.101
_oxdiff_exptl_absorpt_empirical_full_min 0.892