Synthesis, Resolution, and Determination of Absolute Configuration of a Vaulted 2,2'-Binaphthol and a Vaulted 3,3'-Biphenanthrol (VAPOL)

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• 作者：Jianming Bao ; William D. Wulff ; James B. Dominy ; Michael J. Fumo ; Eugene B. Grant ; Alexander C. Rob ; Mark C. Whitcomb ; Siu-Man Yeung ; Robert L. Ostrander ; and Arnold L. Rheingold
• 刊名：Journal of the American Chemical Society
• 出版年：1996
• 出版时间：April 10, 1996
• 年：1996
• 卷：118
• 期：14
• 页码：3392 - 3405
• 全文大小：617K
• 年卷期：v.118,no.14(April 10, 1996)
• ISSN：1520-5126

文摘

Two methods for the synthesis of vaulted biaryls weredeveloped involving the reactions of carbenecomplexes with alkynes and the [2 + 2] cycloaddition of ketenes.The final step in the synthesis of 3,3'-diphenyl-[2,2'-binaphthalene]-1,1'-diol (39) and2,2'-diphenyl-[3,3'-biphenanthrene]-4,4'-diol (47) (VAPOL)was phenol couplingof the 3-phenyl-1-naphthol (14) and the2-phenyl-4-phenanthrol (28), respectively. The naphthol14 could be preparedfrom the thermolysis of phenylacetyl chloride in the presence ofphenylacetylene or from the benzannulation of thepentacarbonyl(phenylmethoxymethylene)chromium(0)(15) with phenylacetylene which upon an acetylativeworkupgives O-acetyl-4-methoxy-2-phenyl-1-naphthol(16). The reductive cleavage of the acetoxy group in16 wasunexpectedly affected by aluminum chloride and ethanethiol which wereused to cleave the methyl ether. In asimilar manner, the phenanthrol 28 could either be preparedfrom the 1-naphthylacetyl chloride (30) orpentacarbonyl(1-naphthylmethoxymethylene)chromium(0) (21).A new procedure for the preparation of carbene complexeswasdeveloped utilizing dimethyl sulfate as methylating agent. Unlikethe benzannulation of the phenyl complex 15,thebenzannulation of the naphthylcarbene complex 21 withphenylacetylene gave a side product which resulted fromthe incorporation of 2 equiv of the alkyne. This side productcould be minimized by the proper control of theconcentration of the alkyne. The phenol coupling of the3-phenyl-1-naphthol with ferric chloride gave2,2'-diphenyl-[2,2'-binaphthalene]-4,4'-diol (38) and with air as oxidantgave the of 3,3'-diphenyl-[2,2'-binaphthalene]-1,1'-diol(39). Oxidative coupling of the 2-phenyl-4-phenanthrol(28) with air gave2,2'-diphenyl-[3,3'-biphenanthrene]-4,4'-diol (47) (VAPOL), but the same coupling with2-tert-butyl-4-phenanthrol (34) failed. The2,2'-binaphthol 39 wasresolved via its cyclic diester with phosphoric acid by salt formationwith (-)-brucine, and the 3,3'-biphenanthrol47was resolved via its cyclic deiester with phosphoric acid(49) by salt formation with (-)-cinchonidine.Theconfiguration of (-)-39 was shown to be S froman X-ray analysis of the brucine salt, and the configurationof(+)-47 was shown to be S from an X-ray analysisthe amide (S,S)-54 derived from49 and (S)--methylbenzylamine.