ライフサイエンスコーパス: diyne

1 gments for the sp2 CH fragment, of 3-ene-1,5-diyne.

2 ery high site selectivity in a coupling of a diyne.

3 lar ring closure reaction of a nonconjugated diyne.

4 ld moieties from one dibenzopentalene to one diyne.

5 zeroth order in nitrile, and zeroth order in diyne.

6 -carbonyl complex on the conjugated enyne or diyne.

7 groups in the biscarbene complex and in the diyne.

8 approach to the synthesis of symmetrical 1,4-diynes.

9 ed cross-benzannulation of cyclic enynes and diynes.

10 regioselectivity is found with unsymmetrical diynes.

11 imethyl carbonate to produce unsymmetric 1,3-diynes.

12 native cyclization of N-tosylated enynes and diynes.

13 u-catalyzed intramolecular hydroarylation of diynes.

14 for the cycloaddition of various ketenes and diynes.

15 enynes but diminishes to 0.5-2 kcal/mol for diynes.

16 that are generated in the cyclization of the diynes.

17 desymmetrization of unprotected tert-hydroxy diynes.

18 xa-1,2,3,5-tetraenes, and (Z)-hexa-3-ene-1,5-diynes.

19 es of Bergman cyclization of (Z)-3-hexen-1,5-diyne (1) at 470 K, the new CC bond retains its energy,

20 hynylbenzene derivative to an organometallic diyne (1,2-diethynyl-3,4-bis(trimethylsilyl)cyclobutadie

21 idyl)ethynyl)bicyclo[2.2.2]oct-1-yl)buta-1,3-diyne, 1, contains two 1,4-bis(ethynyl)bicyclo[2.2.2]oct

22 ization in several highly functionalized 1,n-diynes, 1,n-enynes, and 1,n-allenynes (including 1,2-dip

23 nal functionalization of the known hepta-2,5-diyne-1,7-diol by partial reduction of the two triple bo

24 7 and 29 was accomplished from the key diene-diynes 11 and 19b.

25 hese conditions, conversion of acyclic diene-diyne 16 into tetracyclic system 17 was achieved in 74%

26 Reductive cyclization 1,6-diyne 1a and 1,6-enyne 10a performed under an atmosphere

27 f carbon-, nitrogen- and oxygen-tethered 1,6-diynes 1a-9a and 1,6-enynes 10a-18a using cationic Rh(I)

28 e isomeric diazo compounds, 1-diazo-hexa-2,4-diyne (2) or 2-diazo-hexa-3,5-diyne (3), generates tripl

29 lly initiated topochemical polymerization of diynes 3 and 4a-c in the crystal.

30 The diynes 3,3',5,5'-tetramethyl-4,4'-di(pent-1-ynyl)bipheny

31 diazo-hexa-2,4-diyne (2) or 2-diazo-hexa-3,5-diyne (3), generates triplet carbene 1.

32 sis of (3R,4E,16E,18R)-icosa-4,16-diene-1,19-diyne-3,18-diol, isolated from Callyspongia pseudoreticu

33 ompounds based on an (E)-4,4'-(hexa-3-en-1,5-diyne-3,4-diyl)bis(N,N-bis(4-methoxyphenyl)aniline) skel

34 The (Z)-hex-1,5-diyne-3-ene reactive core common to the enediyne antitum

35 For instance, diyne 6 reacted with dipropylacetylene to give paracyclo

36 For example, diyne 6 reacted with p-tolunitrile in 1,4-dioxane to giv

37 enerated via chemoselective hydroboration of diyne 6 with diisopinocampheylborane.

38 1,2-hydrogen migration to form hex-1-ene-3,5-diyne (6).

39 m the all-carbon analogue, (Z)-hex-3-ene-1,5-diyne (7), the parent molecule for the Bergman cyclizati

40 clusively (44p:44m > 50:1) in 64% yield from diyne 8 and 2-phenylethylisocyanate.

41 t involve reductive coupling of enyne 1a and diyne 9a under an atmosphere of elemental deuterium corr

42 ed hydrogenation of 1,3-enynes 1a-8a and 1,3-diynes 9a-13a at ambient temperature and pressure in the

43 The diyne alcohol 10 was transformed regio- and stereoselect

44 als with bis(pyridyl)oxalamides in which the diyne alignment is near the ideal parameters for topoche

45 ycloaddition of alkynes with fluorinated 1,7-diyne amides gave 4,4-difluoro-1,4-dihydro-3(2H)-isoquin

46 + [2+2+2] sequence using a silyl-substituted diyne and 2 equiv of the corresponding alkyne-nitrile ha

47 between 1,4-bis(diphenylphosphinoyl)buta-1,3-diyne and 9-methylanthracene, such that the bulky methyl

48 The position of the diyne and chain length affect the self-assembling proper

49 hain lengths, substituents, and positions of diyne and studied their self-assembling properties in se

50 Reactions of diynes and aldehydes afforded the [3,3] electrocyclic ri

51 The in situ method also converts diynes and carbon dioxide to the corresponding pyrones.

52 Diynes and cyanamides undergo an iron-catalyzed [2 + 2 +

53 y this procedure to furnish a library of 1,3-diynes and enynes in high yields.

54 Diynes and enynes were used as coupling partners.

55 ve Ni0/NHC catalyst for the cycloaddition of diynes and nitriles that affords pyridines without a dec

56 ation of pyridines from the cycloaddition of diynes and nitriles.

57 olute regiospecific control when symmetrical diynes are applied.

58 seful synthetic handles, and 3-amino skipped diynes are convenient building blocks for enantioselecti

59 bered aryl-substituted ynamides with various diynes are described here.

60 steric effects, while conjugated enynes and diynes are predicted to have increased reactivity and ve

61 as the nitrogen source and activated skipped diynes as the electrophilic reactive partners in a coupl

62 diastereoselective cycloisomerization of 1,6-diynes bearing an alkylidene cyclopropane moiety has bee

63 Upon exposure of 3,4-benzannulated 1,5-diynes (benzo-endiynes) to alpha-ketols (alpha-hydroxyke

64 was observed to result in the 1,11-dien-3,9-diyne benzoate undergoing a more rapid tandem 1,3-acylox

65 d double cycloisomerization of 1,11-dien-3,9-diyne benzoates is described.

66 atalyzed cycloisomerization reactions of 1,7-diyne benzoates to prepare indeno[1,2-c]azepines and aza

67 s of cis-1,8-bis(pyridin-3-oxy)oct-4-ene-2,6-diyne (bpod, 1), [Cu(bpod)(2)]PF(6) (2), and [Cu(bpod)(2

68 alized over the 1,4-di(pyridin-4-yl)buta-1,3-diyne bridges that provide a pathway for electronic comm

69 is-styrenyl bromides lead to unsymmetric 1,3-diynes by the cross coupling of terminal alkyne and the

70 Zirconocene coupling of the diyne (C(6)F(5))C[triple bond]C-1,4-C(6)H(4)-C[triple bo

71 cally coupled triple bonds of conjugated 1,3-diynes can be faithfully discriminated as long as one of

72 /cyclopropenation/Nazarov cyclization of 1,6-diyne carbonates and esters is described.

73 al and achiral tubule-forming molecules, the diynes centered in their hydrocarbon tails.

74 g method using rationally synthesized phenyl-diyne cholesterol (PhDY-Chol) and stimulated Raman scatt

75 through the convergent coupling of a common diyne component with appropriate AB-ring aldehydes, a st

76 Reaction of a mesityl-terminated diyne containing a rigid dihexylfluorenylene spacer with

77 Linear oligophenylene diynes containing 6, 9, and 12 phenylene rings were synt

78 e report here studies of the 4-aza-3-ene-1,6-diyne-containing benzimidazolium salt AZB002 [1-methyl-2

79 and Fmoc-protected derivatives of enyne and diyne coupling products 14b-16b occurs in excellent yiel

80 Platinum-catalyzed diyne cyclization/hydrosilylation tolerated a range of f

81 ted 1,2-dialkylidenecyclopentanes formed via diyne cyclization/hydrosilylation underwent a range of t

82 s a one-pot sequential Zr-mediated oxidative diyne-cyclization/regioselective opening sequence for pr

83 nute advantage for a concerted process; many diyne cycloadditions or aryne cycloreversions will proce

84 enediamine derivative (4) containing a 10,12-diyne-diacyl domain was treated with DTPA anhydride foll

85 Experimental studies on intramolecular diyne + ene cycloadditions show two distinct reaction pa

86 by gold-catalyzed cycloisomerization of 1,6-diyne esters is described.

87 dimethoxy-substituted 3,4-benzocyclodeca-1,5-diyne followed by oxidative demethylation.

88 directly gives the sigma,pi-gold coordinated diyne for the further intramolecular cyclization reactio

89 Using ruthenium(0) catalysts, 1,6-diynes form ruthenacyclopentadienes that engage transien

90 2.2]octane (BCO) chiral rotators linked by a diyne fragment and self-assembles in a one-dimensional,

91 The reaction of unsymmetrical alpha,omega-diynes gave a product only with the substituent adjacent

92 s and subsequent [4 + 2] benzannulation with diynes gives tetrasubstituted benzenes in moderate to go

93 The phenyl-diyne group is biologically inert and provides a Raman s

94 nsitive to the position of the polymerizable diyne group; thus, the polymerization process, typically

95 ng-range carbon atom topomerization in a 1,3-diyne has been demonstrated for the first time.

96 e cross-coupling of alkynes to unsymmetrical diynes has been achieved for the first time.

97 ive enyne CM and RCM reactions involving 1,3-diynes have been developed.

98 es and a smaller number of examples with 1,3-diynes have been reported.

99 A series of trans-enynes and unsymmetric 1,3-diynes have been synthesized by this protocol.

100 he formation of macrocycles from alpha,omega-diynes in cobalt-mediated co-cyclotrimerization reaction

101 giving the desired cross-coupled conjugated diynes in excellent heteroselectivity (>10:1), in good t

102 es to give symmetrical and unsymmetrical 1,3-diynes in good to excellent yields and with good functio

103 ariety of synthetically useful unsymmetrical diynes in good yields.

104 reductive elimination produces a variety of diynes in high yields.

105 Hydrogenation of 1,6-diynes in the presence of alpha-ketoesters provides anal

106 ltrialkylstannes (R(3)Si-SnR'(3)) add to 1,6-diynes in the presence of Pd(0) and tris-pentafluropheny

107 nsubstituted 1-phenyl-4-aryl-3-aza-3-ene-1,4-diynes in which the aryl group is phenyl, o-(methoxy)phe

108 data for a number of different tethered yne-diynes, indicates that the reaction proceeds in a highly

109 ross-coupling reaction producing the desired diyne intermediate 10, while the corresponding omega-est

110 The reactions of enynes and diynes involve 1,4-attack of the Ni-carbonyl complex on

111 ology, a 16-membered cobalt-complexed cyclic diyne is available in 28% yield over eight steps (an ave

112 the hexadehydro-Diels-Alder reaction, a 1,3-diyne is engaged in a [4+2] cycloisomerization with a 'd

113 to generate a structurally rigid, linear 1,3-diyne linkage has been known for over a century.

114 equential enyne ring-closing metathesis of a diyne moiety and metallotropic [1,3]-shift followed by a

115 f the incipient p-benzyne diradical across a diyne moiety of the macrocyclic ring affords an aromatic

116 ydrolytic instability of the 3-aza-3-ene-1,5-diyne moiety prevents its use in pH-triggered DNA cleavi

117 le systems incorporating the 4-aza-3-ene-1,6-diyne moiety were developed.

118 zation, they control the spacing between the diyne monomers to produce an ordered polymer.

119 I)-mediated oxidative cyclization of the 1,6-diyne or 1,6-enyne substrates to afford (hydrido)Rh(III)

120 The reaction of dodec-11-ene-1,6-diynes or their heteroatom congeners with a hydrosilane

121 d-chelate lipid and a commercially available diyne-PE was formulated as a liposome suspension and irr

122 38, and 40 were prepared from similar diene-diyne precursors via the tandem Pauson-Khand cyclization

123 tial intramolecular oxidative cyclization of diyne produces the nickelacyclopentadiene intermediate.

124 The diynes required for this procedure are readily synthesiz

125 opyl aryl substituent to either the enyne or diyne substrate.

126 These diene-diyne substrates are found to undergo a highly chemosele

127 ition and cyclization reactions of enyne and diyne substrates assembled on a tert-butylsulfinamide ly

128 ty patterns observed with different types of diyne substrates in gold catalysis are discussed.

129 ic quantities of amino-substituted enyne and diyne substrates to ((iPr(TB))PDI)Fe(N2)2 resulted in is

130 Diynes synthesized by this methodology were readily zirc

131 st an unprecedented oxidative cyclization of diynes takes place.

132 1-Phenyl-4-aryl-3-aza-3-ene-1,5-diynes that lack a 6-substituent undergo aza-Bergman cyc

133 Diynes that possessed an electron-deficient internal alk

134 Diynes that possessed propargylic substitution underwent

135 ranging from 80% to 89%, whereas icosa-5,15-diyne (the dimer obtained from a 1-halo-5-decyne) is fou

136 ution on the cycloaromatization of 3-ene-1,5-diynes (the Bergman cyclization).

137 selectivity inherent to these chiral skipped diynes, the reaction tolerates an extremely broad substr

138 amolecular propargylic ene reaction of a 1,6-diyne to generate a vinylallene, which then reacts in an

139 elective (83-95% ee) addition of various 1,3-diynes to aldehydes of diverse structures.

140 d for the catalytic addition of terminal 1,3-diynes to aldehydes was developed using our dinuclear zi

141 A new asymmetric [2+2+2] cycloaddition of diynes to sulfonimines under rhodium catalysis that prov

142 A Ni/N-heterocyclic carbene catalyst couples diynes to the C(alpha)-C(beta) double bond of tropone, a

143 ross-benzannulation of conjugated enynes and diynes under cobalt-catalysis led to 1,2,3-trisubstitute

144 A cool break: 3-Azetidinone and a variety of diynes undergo a cycloaddition reaction catalyzed by Ni/

145 For example, 3-aza-3-ene-1,5-diynes undergo an aza-Bergman cyclization to afford the

146 In co-crystals with one oxalamide host, the diyne undergoes spontaneous topochemical polymerization

147 Long-chain alpha,omega-diynes underwent metal-mediated [2 + 2 + 2] cycloadditio

148 nnulenes incorporating strained 1,4-buta-1,3-diyne units have been synthesized, where m = 2, n = 14 (

149 ke nanoribbon (GDNR) bearing both alkyne and diyne units, allowing for multichannel pi-conjugation, w

150 cloaddition with substrates containing three diyne units.

151 yzed synthesis of nonracemic 3-amino skipped diynes via an enantiodetermining C-C bond formation is d

152 t silver-catalyzed desymmetrization of amino diynes via hydroamination is reported.

153 After the corresponding 1,6-diyne was generated in situ, cyclization afforded the de

154 cyclization of 1,4-diphenyl-3-aza-3-ene-1,5-diyne was investigated.

155 Moreover, the use of unsymmetrical diynes was investigated, resulting in the formation of t

156 or the cyclization of (3Z)-cyclodec-3-en-1,5-diyne were carried out to investigate heavy-atom tunneli

157 Many different diynes were efficiently coupled to afford [5-6-7] fused

158 t unsymmetrically substituted naphthyl-based diynes were synthesized.

159 Cyclic reactants (enynes and diynes) were readily prepared in reasonable yields from

160 the reaction of a biscarbene complex with a diyne, which generates two of the benzene rings and the

161 lyl)ethynyl)bicyclo[1.1.1]pent-1-yl)buta-1,3-diyne, whose bicyclopentane units can rotate but are ach

162 to co-cyclotrimerize long-chain alpha,omega-diynes with alkynes in certain cases to demonstrate a su

163 r- and intramolecular [2+2+2] cyclization of diynes with alpha,beta-unsaturated enones proceeds with

164 cross [2 + 2 + 2] cyclotrimerizations of 1,6-diynes with cyclic and acyclic double bonds.

165 onent higher order cycloaddition of tethered diynes with cyclic trienes that generates five rings and

166 d [2+2+2] cyclotrimerizations of alpha,omega-diynes with isocyanates, isothiocyanates, and carbon dis

167 mediated reductive cyclization of enynes and diynes with turnover frequencies comparable to those of

168 amolecular reductive cyclization of an oligo(diyne) with a low-valent zirconocene reagent, which give

169 Diyne + yne cycloadditions connect with arynes and ethyn

170 The first examples of 1,3-diyne + yne cycloadditions to give o-benzynes were repor