Benzo/Naphtho‐Anellated Dihydro‐1, 2‐oxaphosphinines and Ring‐Opening to P‐Tertiary 2‐Phosphanyl‐1, 1′‐biaryl‐2‐ol Derivatives – Syntheses and Structures. Issue 29 (10th August 2017)

• Record Type: Journal Article
• Authors: Wawrzyniak, Piotr; Kindermann, Markus K.; Thede, Gabriele; Schulzke, Carola; Jones, Peter G.; Heinicke, Joachim W.
• Is Part Of: European journal of inorganic chemistry. Issue 29(2017)
• Page Start: 3580
• Page End: 3586
• Publication Date: 2017-08-10
• Subjects: P, O heterocycles -- Phosphanes -- P ligands -- Chirality -- Diastereoisomers; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201700770
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Reaction of naphthylphenol1a and phenylnaphthol1b, respectively, with PCl3 in the presence of ZnCl2 gave mixed benzo‐ and naphtho‐anellated 6‐chloro‐6 H ‐1, 2‐oxaphosphinines2a and2b . Treatment with equimolar amounts of t BuLi led to 6‐ t Bu‐substituted mixed‐anellated oxaphosphinines3a and3b, respectively, and subsequent P–O‐ring cleavage with methyllithium and quenching with ClSiMe3 to 2‐trimethylsilyloxy‐biarylphosphanes4a and4b . NMR spectra indicated two data sets for4a but only one for4b, indicating higher diastereoselectivity in the ring opening of the 1, 2‐oxaphosphinine3b with oxygen in 2‐position of naphthalene and the bulkier t BuMeP‐group at the phenyl ring. Reaction of2b with o ‐anisyllithium (2 equiv.) and ClSiMe3 led to the biarylsilyl ether5b . Further conversion with (1 S )‐camphanoyl chloride gave diastereoisomers of the 2′‐phosphanylbiaryl camphanate6b . Structures were proven by characteristic multinuclear NMR spectroscopic data and for2a and5d by crystal structure analysis.5b and6b might be useful candidates for enantiomer separation and asymmetric transition metal catalysis. Abstract : A synthetic route to mixed benzo/naphtho‐anellated 2 H ‐1, 2‐oxaphosphinines and to first examples of benzo/naphtho‐biaryl‐P, O hybrid ligands is reported. The new compounds were characterized by NMR spectroscopic data and single crystal structures of a 2‐chloro‐benzo/naphtho‐1, 2‐oxaphosphinine and a siloxy‐biaryldianisylphosphane.