Applications of C-h functionalization logic to cyclobutane synthesis.
Gutekunst, Will R.; Baran, Phil S.; The Journal of organic chemistry 79 (2014) 2430–2452; doi:10.1021/jo4027148

data_4029190
_publ_section_title
;
 Applications of C-h functionalization logic to cyclobutane synthesis.
;
_journal_issue                   6
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              2430
_journal_page_last               2452
_journal_paper_doi               10.1021/jo4027148
_journal_volume                  79
_journal_year                    2014
_chemical_formula_moiety         'C98 H98 N8 O18 Pd1 S4 Si2, 3(C H2 Cl2)'
_chemical_formula_sum            'C101 H104 Cl6 N8 O18 Pd S4 Si2'
_chemical_formula_weight         2221.44
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-11-20
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2013.11.15 svn.r2834 for OlexSys, GUI svn.r4713)
;
_cell_angle_alpha                74.962(3)
_cell_angle_beta                 85.165(3)
_cell_angle_gamma                66.031(3)
_cell_formula_units_Z            2
_cell_length_a                   14.882(4)
_cell_length_b                   15.800(4)
_cell_length_c                   25.597(7)
_cell_measurement_reflns_used    9944
_cell_measurement_temperature    100
_cell_measurement_theta_max      25.338
_cell_measurement_theta_min      2.454
_cell_volume                     5310(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2013.10-0 (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX CCD'
_diffrn_detector_area_resol_mean 8.0
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_device       'Fixed Chi Three-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker D8 APEX'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0374
_diffrn_reflns_av_unetI/netI     0.0600
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            36839
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.393
_diffrn_reflns_theta_min         0.824
_diffrn_source                   'sealed tube'
_diffrn_source_type              fine-focus
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.495
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.5669
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0795 before and 0.0575 after correction.
The Ratio of minimum to maximum transmission is 0.7607.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            Colorless
_exptl_crystal_colour_primary    Colorless
_exptl_crystal_density_diffrn    1.389
_exptl_crystal_description       Block
_exptl_crystal_F_000             2300
_exptl_crystal_size_max          0.345
_exptl_crystal_size_mid          0.227
_exptl_crystal_size_min          0.189
_refine_diff_density_max         1.504
_refine_diff_density_min         -2.166
_refine_diff_density_rms         0.126
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.227
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1379
_refine_ls_number_reflns         19033
_refine_ls_number_restraints     385
_refine_ls_restrained_S_all      1.218
_refine_ls_R_factor_all          0.1345
_refine_ls_R_factor_gt           0.1189
_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^)+(0.0351P)^2^+57.7038P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2544
_refine_ls_wR_factor_ref         0.2628
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16201
_reflns_number_total             19033
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo4027148_si_002.cif
_cod_data_source_block           Baran165
_cod_depositor_comments
;
The following automatic conversions were performed:

'_diffrn_radiation_probe' value 'X-ray' changed to 'x-ray' according
to
/usr/data/users/saulius/crontab/automatic-downloads/current/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 2281 2013-09-26 08:29:07Z andrius 
;
_cod_database_code               4029190
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.912
_shelx_estimated_absorpt_t_min   0.848
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C31B-C32B = C31B-C33B = C31B-C34B
 1.54 with sigma of 0.02
 Cl3S-C2S = Cl3B-C2SB = Cl4B-C2SB = Cl4S-C2S
 1.8 with sigma of 0.02
 Cl8S-C3S = Cl9S-C3S = Cl10-C3S = Cl5S-C3S = Cl6S-C3S = Cl7S-C3S
 1.8 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Si1B) = Uanis(Si1)
Uanis(C22B) = Uanis(C22')
Uanis(S1B') = Uanis(S1')
Uanis(O6B') = Uanis(O6')
Uanis(O5') = Uanis(O5B')
Uanis(C27B) = Uanis(C27')
Uanis(C26B) = Uanis(C26')
Uanis(C25B) = Uanis(C25')
Uanis(C28B) = Uanis(C28')
Uanis(C24') = Uanis(C22')
Uanis(C23') = Uanis(C23B)
Uanis(Cl1S) = Uanis(Cl1B)
Uanis(C1SB) = Uanis(C1S)
Uanis(Cl2B) = Uanis(Cl2S)
Uanis(C24B) = Uanis(C24')
Uanis(N4B) = Uanis(N4)
Uanis(S2) = Uanis(S2B)
Uanis(O8B) = Uanis(O8)
Uanis(O9B) = Uanis(O9)
Uanis(C43) = Uanis(C43B)
Uanis(C48B) = Uanis(C48)
Uanis(C47B) = Uanis(C47)
Uanis(C46B) = Uanis(C46)
Uanis(C49B) = Uanis(C49)
Uanis(C45B) = Uanis(C45)
Uanis(C44B) = Uanis(C44)
Uanis(O7B) = Uanis(O7)
Uanis(Si1) = Uanis(Si1B)
Uanis(C32B) = Uanis(C30)
Uanis(C33B) = Uanis(C29)
Uanis(C34B) = Uanis(C34)
Uanis(C31B) = Uanis(C31)
Uanis(C33) = Uanis(C30B)
Uanis(C32) = Uanis(C29B)
Uanis(Cl3S) = Uanis(Cl3B) = Uanis(Cl4S) = Uanis(Cl4B) = Uanis(C2S)
Uanis(C2SB) = Uanis(C2S)
Uanis(C3S) = Uanis(Cl7S) = Uanis(Cl6S) = Uanis(Cl5S) = Uanis(Cl10) =
Uanis(Cl9S) = Uanis(Cl8S)
4. Rigid body (RIGU) restrains
 O5', S1', O6', C22', C23', C24', C25', C28', C26', C27'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O5B', O6B', S1B', C22B, C23B, C22', C25B, C26B, C27B, C28B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4, S2, O8, O9, C43, C48, C47, C46, C45, C44, C49
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4B, S2B, O9B, O8B, C43B, C48B, C47B, C46B, C45B, C44B, C49B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Si1, C29, C30, C31, C34, C33, C32
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C29B, Si1B, C30B, C31B, C34B, C32B, C33B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Si1B)=Sof(C29B)=Sof(H29D)=Sof(H29E)=Sof(H29F)=Sof(C30B)=Sof(H30D)=
 Sof(H30E)=Sof(H30F)=Sof(C31B)=Sof(C32B)=Sof(H32D)=Sof(H32E)=Sof(H32F)=
 Sof(C33B)=Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(C34B)=Sof(H34D)=Sof(H34E)=
 Sof(H34F)=1-FVAR(1)
 Sof(Si1)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C30)=Sof(H30A)=Sof(H30B)=
 Sof(H30C)=Sof(C31)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33)=Sof(H33A)=
 Sof(H33B)=Sof(H33C)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=FVAR(1)
 Sof(S1B')=Sof(O5B')=Sof(O6B')=Sof(C22B)=Sof(C23B)=Sof(H23B)=Sof(C24B)=
 Sof(H24B)=Sof(C25B)=Sof(C26B)=Sof(H26B)=Sof(C27B)=Sof(H27B)=Sof(C28B)=
 Sof(H28G)=Sof(H28H)=Sof(H28I)=1-FVAR(2)
 Sof(S1')=Sof(O5')=Sof(O6')=Sof(C22')=Sof(C23')=Sof(H23')=Sof(C24')=Sof(H24')=
 Sof(C25')=Sof(C26')=Sof(H26')=Sof(C27')=Sof(H27')=Sof(C28')=Sof(H28D)=
 Sof(H28E)=Sof(H28F)=FVAR(2)
 Sof(Cl1B)=Sof(Cl2B)=Sof(C1SB)=Sof(H1SC)=Sof(H1SD)=1-FVAR(3)
 Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(Cl1S)=Sof(Cl2S)=FVAR(3)
 Sof(O7B)=Sof(H10A)=1-FVAR(4)
 Sof(O7)=Sof(H10)=FVAR(4)
 Sof(S2B)=Sof(O8B)=Sof(O9B)=Sof(N4B)=Sof(H36A)=Sof(C43B)=Sof(C44B)=Sof(H44B)=
 Sof(C45B)=Sof(H45B)=Sof(C46B)=Sof(C47B)=Sof(H47B)=Sof(C48B)=Sof(H48B)=
 Sof(C49B)=Sof(H49D)=Sof(H49E)=Sof(H49F)=1-FVAR(5)
 Sof(S2)=Sof(O8)=Sof(O9)=Sof(N4)=Sof(H36)=Sof(C43)=Sof(C44)=Sof(H44)=Sof(C45)=
 Sof(H45)=Sof(C46)=Sof(C47)=Sof(H47)=Sof(C48)=Sof(H48)=Sof(C49)=Sof(H49A)=
 Sof(H49B)=Sof(H49C)=FVAR(5)
 Fixed Sof: C2S(0.75) H2SA(0.75) H2SB(0.75) Cl3B(0.25) Cl3S(0.75) Cl4B(0.25)
 Cl4S(0.75) C2SB(0.25) H2SC(0.25) H2SD(0.25) H3SC(0.33333) H3SD(0.33333)
 H3SA(0.33333) H3SB(0.33333) H3SF(0.33333) H3SE(0.33333) Cl5S(0.41783)
 Cl6S(0.3173) Cl7S(0.39492) Cl8S(0.25316) Cl9S(0.27413) Cl10(0.34266)
6.a Ternary CH refined with riding coordinates:
 C9(H9), C10(H10), C10(H10A), C11(H11), C9'(H9'), C10'(H10'), C11'(H11')
6.b Secondary CH2 refined with riding coordinates:
 C1S(H1SA,H1SB), C1SB(H1SC,H1SD), C2S(H2SA,H2SB), C2SB(H2SC,H2SD), C3S(H3SC,
 H3SD), C3S(H3SA,H3SB), C3S(H3SF,H3SE)
6.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C15(H15), C18(H18), C19(H19), C20(H20),
 C21(H21), C23(H23), C24(H24), C26(H26), C27(H27), C36(H36), C36(H36A),
 C39(H39), C40(H40), C41(H41), C42(H42), C44(H44), C44B(H44B), C45(H45),
 C45B(H45B), C47(H47), C47B(H47B), C48(H48), C48B(H48B), C1'(H1'), C2'(H2'),
 C3'(H3'), C4'(H4'), C15'(H15'), C18'(H18'), C19'(H19'), C20'(H20'), C21'(H21'),
  C23'(H23'), C23B(H23B), C24'(H24'), C24B(H24B), C26'(H26'), C26B(H26B),
 C27'(H27'), C27B(H27B), C36'(H36'), C39'(H39'), C40'(H40'), C41'(H41'),
 C42'(H42'), C44'(H44'), C45'(H45'), C47'(H47'), C48'(H48')
6.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C29B(H29D,H29E,
 H29F), C30(H30A,H30B,H30C), C30B(H30D,H30E,H30F), C32(H32A,H32B,H32C),
 C32B(H32D,H32E,H32F), C33(H33A,H33B,H33C), C33B(H33D,H33E,H33F), C34(H34A,H34B,
 H34C), C34B(H34D,H34E,H34F), C49(H49A,H49B,H49C), C49B(H49D,H49E,H49F),
 C13'(H13D,H13E,H13F), C28'(H28D,H28E,H28F), C28B(H28G,H28H,H28I), C29'(H29G,
 H29H,H29I), C30'(H30G,H30H,H30I), C32'(H32G,H32H,H32I), C33'(H33G,H33H,H33I),
 C34'(H34G,H34H,H34I), C49'(H49G,H49H,H49I)
;
_shelx_res_checksum              86206
_shelx_hkl_checksum              24956