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P−H‐Functionalized Phosphanyl Alcohols: RHPCH 2 CHMeOH and 2‐PHR‐1‐OH‐cyclo‐C 6 H 10 (R = Ph, 2,4,6‐Me 3 C 6 H 2 , 2,4,6‐ i Pr 3 C 6 H 2 ) and Molecular Structures of (C R ,C R ,P R /C S ,C S ,P S )‐2‐PH(2,4,6‐ i Pr 3 C 6 H 2 )‐1‐OH‐cyclo‐C 6 H 10 and its Dilithio Salt [Li 2 (THF) 0.5 {(C R ,C R /C S ,C S )‐2‐P(2,4,6‐ i Pr 3 C 6 H 2 )‐1‐O‐cyclo‐C 6 H 10 }] 4
Author(s) -
Koch Thomas,
Blaurock Steffen,
Somoza, Jr. Fernando,
HeyHawkins Evamarie
Publication year - 2000
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200010)2000:10<2167::aid-ejic2167>3.0.co;2-c
Subject(s) - chemistry , diastereomer , deprotonation , cyclohexene oxide , medicinal chemistry , stereochemistry , carboxylate , cyclohexene , organic chemistry , catalysis , ion
The P−H‐functionalized phosphanyl alcohols RHPCH 2 CHMeOH [R = Ph ( 1 ), 2,4,6‐Me 3 C 6 H 2 (Mes) ( 2 ), 2,4,6‐ i Pr 3 C 6 H 2 (Tipp) ( 3 )] and 2‐PHR‐1‐OH‐cyclo‐C 6 H 10 [(R = Ph ( 4 ), Mes ( 5 ), Tipp ( 6 )] have been prepared by ring‐opening of propene oxide or cyclohexene oxide, respectively, with the appropriate LiPHR species, followed by hydrolytic workup and distillation ( 1−4 ) or recrystallization ( 5 , 6 ). 1−6 , which were obtained as diastereomeric mixtures, have been characterized spectroscopically ( 1 H, 13 C, 31 P NMR, IR, MS). Only in the case of 6 could separation of the diastereomers be achieved by fractional crystallization and the molecular structure of the racemic isomer (C R ,C R ,P R /C S ,C S ,P S ) has been determined. In situ double deprotonation of 1 − 6 with BuLi gave the corresponding dianions 1a − 6a . The molecular structure of the dilithio salt [Li 2 (THF) 0.5 {(C R ,C R /C S ,C S )‐2‐P(2,4,6‐ i Pr 3 C 6 H 2 )‐1‐O‐cyclo‐C 6 H 10 }] 4 ( 6a ) has been determined and shows that it is tetrameric in the solid state with a central Li 8 cluster.