Diels-Alder reaction 10.2- camphorsultam

Oppolzefs chiral auxiliary,6 (-)-2,10-camphorsultam, is useful in the asymmetric Diels-Alder reaction,3 4 and for the preparation of enantiomerically pure p-substituted carboxylic acids7 and diols,8 in the stereoselective synthesis of A2-isoxazolines,9 and in the preparation of N-fluoro (-)-2,10-camphorsultam, an enantioselective fluorinating reagent.10... 

Thermal reactions of Al-enoylsultams generally show only moderate endo and r-face selectivity, e.g. Al-acryloyl- and N-crotonoyl-10,2-camphorsultams (4) and (6) with cyclopentadiene (eq 3, Table 1). The thermal hetero-Diels-Alder reaction of Al-glyoxaloyl-10,2-camphorsultam with 1-methoxybuta-... 

Cycloadditions (Athene Five-Membered Cyclo-adduct) The levels of selectivity found for 1,3-dipolar cycloaddition reactions are not as high as those obtained for Lewis acid-catalyzed Diels-Alder reactions. However, the 10,2-camphorsultam auxiliary can achieve synthetically useful levels of induction in these reactions, and this has been attributed to efficient enoyl conformational control by the sultam moiety leading to preferred C(a)-re face attack even in the absence of metal complexation. ... 

Diels-Alder Cycloadditions (AUcene -+ Six-Membered Cycloadduct). lV-Acryloyl-a-methyltoluene-2,a-sultam (3a) participates in highly endo and C(a)-re ir-face selective Lewis acid promoted Diels-Alder reactions with Cyclopentadiene, 1,3-Butadiene, and Isoprene (eq 2 and Table 1). These levels of induction compare favorably with most alternative auxiliaries, including the 10,2-camphorsultam. However, V-crotonyl-a-methyltoluene-2,a-sultam (ent-3b) reacts with cyclopentadiene with only mod-... 

The intermediate sulfonimide derived from saccharin by addition of an alkyllithium compound is also the starting material for sultams mimicking the behavior of camphorsultams. The sultams arc readily obtained from, e.g., 3-methylbenzisothiazole 1,1-dioxide, by ruthenium-catalyzed enantioselective reduction, using BINAP as a chiral ligand, in enantiomerically pure form 79. Thus, both enantiomers can be obtained by using the appropriate enantiomer of the control ligand. Like the camphorsultams, the saccharin derivatives readily form amides with carboxylic acids which can be alkylated via the carbanion (Section D.1.1.1.3.1.) or, if unsaturated carboxylic acids are used, may react as chiral dienophiles in Diels—Alder reactions (Section D.l.6.1.1.1.). 

As one of the pioneering works on asymmetric synthesis, Evans and coworkers reported diastereoselective Diels-Alder reaction of acryloyl oxazolidinones mediated by Et2AlCl [140]. Intramolecular version of this cycloaddition was also reported, in which interesting stereochemical difference depending on substituents at oxazo-lidinone ring was found. As an another excellent example, Oppolzer and coworkers reported diastereoselective Diels-Alder reaction of chiral dienophiles equipped with camphorsultam auxiliary [141]. Recently, these diastereoselective reactions were applied to enantioselective synthesis of ceralure Bl, known as Mediterranean fruit fly attr actant (Scheme 6.118) [142]. 

The use of amides and imides as chiral auxiliaries in [4 + 2]-cycloadditions has been the subject of numerous investigations. Oppolzer reported the use of camphorsultam 112 in asymmetric Diels-Alder reactions [26, 67. 68], The camphor sultam is readily available in both enantiomeric forms from cam-phorsulfonyl chloride. Acrylate 113 was found to react with cyclopentadiene in the presence of EtAlCl2 to give 115 with high selectivity (endo/exo = 99.5 0.5, dr = 97.5 2.5, Equation 10) [67]. Oppolzer also reported that triene 116 participated in an intramolecular Diels-Alder cycloaddition reaction to afford endo product 117 in 71 % yield and 96.5 3.5 dr (Scheme 17.19) [69]. This bicyclic product was subsequently converted into the pyridine alkaloid (-)-pulo upone (118). 

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